Hydrohalogenation Of Vinyl-Terminated Macromonomers And Functionalized Derivatives

ABSTRACT

This invention relates to a polyolefin composition comprising one or more of the following formulae: 
     
       
         
         
             
             
         
       
     
     wherein the PO is the residual portion of a vinyl terminated macromonomer (VTM) having had a terminal unsaturated carbon of an allylic chain and a vinyl carbon adjacent to the terminal unsaturated carbon; X is attached to the terminal portion of the VTM to provide PO—X or at the vinylidene carbon of the VTM to provide PO—CHXCH 3 ; and X is Cl, Br, I, or F.

CROSS-REFERENCE TO RELATED APPLICATION

This application claims priority to and the benefit of U.S. ProvisionalApplication No. 61/704,743, filed Sep. 24, 2012, the disclosure of whichis incorporated herein by reference in its entirety.

FIELD OF THE INVENTION

This invention relates to functionalization of vinyl terminatedpolyolefins by hydrohalogenation.

BACKGROUND OF THE INVENTION

Methods for the production of polyolefins with end-functionalized groupsare typically multi-step processes that often create unwantedby-products and waste of reactants and energy. For reviews of methods toform end-functionalized polyolefins, see: (a) S. B. Amin and T. J.Marks, Angewandte Chemie, International Edition, 2008, 47, pp.2006-2025; (b) T. C. Chung Prog. Polym. Sci. 2002, 27, pp. 39-85; (c) R.G. Lopez, F. D'Agosto, C. Boisson Prog. Polym. Sci. 2007, 32, pp.419-454. A process with a reduced number of steps, even one step, wouldbe desirable.

U.S. Pat. No. 4,110,377 discloses secondary aliphatic amines alkylatedwith alpha-olefins, such as ethylene, propylene, hexene, and undecene.Likewise, several literature references disclose hydroaminoalkylation ofolefins using various catalysts (see J. Am. Chem. Soc. 2008, 130, pp.14940-14941; J. Am. Chem. Soc. 2007, 129, pp. 6690-6691; AngewandteChemie, International Edition, 2009, 48, pp. 8361-8365; AngewandteChemie, International Edition, 2009, 48, pp. 4892-4894; Yuki GoseiKagaku Kyokaishi (2009), 67(8), pp. 843-844; Angewandte Chemie,International Edition (2009), 48(6), pp. 1153-1156; Tetrahedron Letters(2003), 44(8), pp. 1679-1683; Synthesis (1980), (4), pp. 305-306). Coreydiscloses low molecular weight olefins treated with hydrosilanes in thepresence of Cp₂MCl₂ and n-BuLi to prepare low molecular weighthydrosilylated products.

None of the above references however disclose functionalization ofpolyolefins, particularly polyolefins having Mn's over 500 g/mol havinglarge amounts of vinyl terminal groups.

U.S. Pat. No. 8,399,725 discloses certain vinyl terminated polymers thatare functionalized, optionally, for use in lubricant applications.

U.S. Pat. No. 8,372,930 discloses certain vinyl terminated polymers thatare functionalized in U.S. Pat. No. 8,399,725.

U.S. Pat. No. 8,283,419 discloses a process to functionalize propylenehomo- or copolymer comprising contacting an alkene metathesis catalystwith a heteroatom containing alkene and a propylene homo- or copolymerhaving terminal unsaturation.

Additional references of interest include Kropp Paul J. et al J. Am.Chem. Soc. 1990, 112, pp. 7433-7434) and Kennedy, J. P. in US2011/0082259 (“Singly-Terminated Polyisobutylenes and Process for MakingSame”), Journal of Polymer Science: Part A: Polymer Chemistry, 2008, 46,pp. 4236-4242 (“Quantitative Syntheses of Novel Polyisobutylenes Fittedwith Terminal Primary —Br, —OH, —NH2, and Methacrylate Termini”); U.S.Pat. Nos. 6,111,027; 7,183,359; 6,100,224; and 5,616,153.

Thus, there is a need to develop a means to provide functionalizedpolyolefins (particularly end-functionalized) by efficient reactions,particularly reactions with good conversion, preferably under mildreaction conditions with a minimal number of steps, preferably one ortwo steps. The instant invention's use of hydrohalogenation to introducea halogen functionality is both a commercially economical and an“atom-economical” route to end-functionalized polyolefins.

End-functionalized polyolefins that feature a chemically reactive orpolar end group are of interest for use in a broad range of applicationsas compatibilizers, tie-layer modifiers, surfactants, adhesives, andsurface modifiers. Herein is described a novel method for theirproduction by the reaction of vinyl-terminated polyolefins withhydrohalogenated materials. This method is useful for a range of vinylterminated polyolefins, including isotactic polypropylene (iPP), atacticpolypropylene (aPP), ethylene propylene copolymer (EP), polyethylene(PE), and particularly propylene copolymers with larger alpha-olefincomonomers such as butene, hexene octene, etc. The vinyl terminatedpolyolefin useful herein can be linear or branched.

SUMMARY OF THE INVENTION

This invention relates to a polyolefin composition comprising one ormore of the following formulae:

wherein the PO is the residual portion of a vinyl terminatedmacromonomer (VTM) having had a terminal unsaturated carbon of anallylic chain and a vinyl carbon adjacent to the terminal unsaturatedcarbon;X is attached to the terminal portion of the VTM to provide PO—X or atthe vinylidene carbon of the VTM to provide PO—CHXCH₃; and

X is Cl, Br, I, or F.

Hydrohalogenation of vinyl terminated macromonomers have been shown,inter alia, herein to give the corresponding bromo terminated polyolefinfor polypropylene, C₃C₄, and C₃C₆ copolymers having high vinyl contentin the chain end. The bromination method uses simple and inexpensivereagents and affords products in high yield, purity, andregioselectivity. These polyolefin bromides have been furtherderivitized herein with common nucleophiles such as amines, polyamines,amino alcohols, polyetheramines, polyols, polyalkylene glycol, andhydroxide for introducing heteroatom polar functionalities. Theresulting functionalized materials are useful additives and can serve asdispersants, corrosion inhibitors, detergents, surfactants andemulsifier, etc in engine oil, refinery, and oil field chemicalsindustries.

Efficient and quantitative synthesis of bromine- or other halogen-(chlorine, iodine, or fluorine) terminated polyolefins such as thefollowing:

from vinyl-terminated macromonomers (VTMs) as the terminally unsaturatedpolyolefins. A simple and inexpensive method for functionalizing VTMswith a bromo group in high yield and purity is disclosed. Thesebromo-terminated macromers can be subsequently used for faciletransformation into a diverse range of functional groups and/or morecomplex polymeric architectures (e.g., block copolymer structures)through (i) substitution reactions, or (ii) formation of organometallicreagents, or (iii) optionally coupling with another polyolefin block.For example, the halogen-terminated polyolefins can be easilyfunctionalized.

Polyolefin bromides are synthesized by hydrobromination of a number ofhigh vinyl content terminated macromonomers (C₃, C₃C₄, C₃C₆) withdifferent backbone composition and molecular weights in high yield,purity, excellent regioselectivity and short reaction time. Addition ofthe hydrogen bromide (HBr) molecule across the double bond of the vinylgroup at the chain end takes place predominantly in the so-calledanti-Markovnikov fashion (i.e., the bromine atom is added to theterminal carbon of the vinyl group and the hydrogen to the adjacentinternal carbon), resulting in the formation of a primary bromide(—CH₂—Br) structure at the chain end of the polyolefin. The bromidesformed in this addition reaction may be conveniently calledbromo-terminated macromonomers. The versatility and utility of thebromides are further demonstrated by reactions with nucleophiles toafford the corresponding terminally functionalized polyolefin moleculesin high yield and purity under mild reaction conditions.

BRIEF DESCRIPTION OF THE FIGURES

FIG. 1 is a ¹H NMR spectrum of the product 2 from Example 3.

DETAILED DESCRIPTION OF THE INVENTION

The hydrobromination functionalization method as applied to VTMsdescribed herein affords the 1-bromo polyolefin in highregioselectivity, presumably as result of a peroxide effect. The sourceof the peroxide is believed to be the result of exposure of the VTMmaterials to open atmosphere leading to the formation of trace amount ofperoxide in the material. No additional peroxide radical initiator isneeded for the reaction to follow a radical addition mechanism. It isalso understood that an ionic mechanism would lead to the 2-bromopolyolefin regioisomer via the intermediacy of a secondary carbocation.In other words, if the 2-bromo regioisomer is the desired product, theVTM materials and hydrogen bromide reagent is preferably purified toeliminate traces of peroxide species.

Common nucleophiles such as hydroxide and alkoxides can be used forillustration and other nucleophiles may also be used for introducingheteroatom polar functionalities. A non-exhaustive list of carbon,nitrogen, oxygen, phosphorus, and sulfur nucleophiles are providedbelow.

Examples of carbon nucleophiles bearing acidic hydrogen(s) include butare not limited to dialkyl malonate, cyano ester, malononitrile,1,3-diketone, cyanide, the alpha-carbanion of ketone, aldehydes, esters,nitriles, anions of terminal alkynes, phosphonate, phosphonium salts,sulfoxide anions, sulfone anions, cyclopentadienyl anions, indenylanions, fluorenyl anions, alkyl metals, vinyl metals, aryl metals,heteroaryl metal reagents derived from Grignard reagents, organolithiumreagents, organozinc reagents or organocuprate reagents, and the like.

Examples of nitrogen nucleophiles include, but are not limited to,pyridine, quinoline, pyrrole, or imidazole.

Examples of oxygen nucleophiles include, but are not limited to, water,hydroxide anion, alkoxide anions, phenoxide anions, naphthoxide anions,carboxylate anion (acetate, propanoate, benzoate, acrylate,methacrylate), or hydrogen peroxide.

Examples of phosphorus nucleophiles include, but are not limited to,trialkyl phosphite, triaryl phosphite, trialkyl phosphine, triarylphosphine, dialkyl phosphine, and diaryl phosphine.

Examples of sulfur nucleophiles include, but are not limited to,hydrogen sulfide and its salts, alkyl monothiols and thiolate anions,aromatic monothiol, thiourea, thiol carboxylic acid (e.g., thioaceticacid salt, RC(═O)—S⁻), xanthate anion (dithiocarbonate, RO—C(═S)—S⁻,e.g., from alcohol, KOH and carbon disulfide), or dithiocarbamate anionR₂N—C(═S)—S⁻.

In addition to participating in nucleophilic substitution reaction wherethe bromide is acting as a good leaving group, the bromine group on thepolyolefin can be used for the formation of organometallic reagentsthrough transmetallation (e.g., lithiation with n-butyllithium orsec-butyllithium or tert-butyllithium), oxidative addition with metal(e.g., zinc, magnesium and other activated metal). The newly formedpolyolefin organometallic reagent will be turned into a strongnucleophile for undergoing (i) nucleophilic addition to electrophiles(e.g., aldehyde, ketone, ester, thioester, anhydride, nitrile, epoxide,acetal, organic halide, etc.); (ii) transition metal catalyzedcross-coupling with alkyl, vinyl, aryl, heteroaryl halides; and (iii)cross-coupling with another polymer block bearing any of the saidfunctional group(s) mentioned above to form a diblock or multi-blockcopolymer structures. Examples of chain-end functionalized polymerincludes bromo terminated polystyrene or polyolefin derived from VTMs(polypropylene, EP, propylene/alpha olefin copolymer, polyalphaolefin,etc).

DEFINITIONS

In the structures depicted throughout this specification and the claims,a solid line indicates a bond, and an arrow indicates that the bond maybe dative.

As used herein, the new notation for the Periodic Table Groups is usedas described in Chemical and Engineering News, 63(5), p. 27 (1985).

The term “substituted” means that a hydrogen group has been replacedwith a hydrocarbyl group, a heteroatom, or a heteroatom containinggroup. For example, methyl cyclopentadiene (Cp) is a Cp groupsubstituted with a methyl group and ethyl alcohol is an ethyl groupsubstituted with an —OH group.

The terms “hydrocarbyl radical,” “hydrocarbyl,” and “hydrocarbyl group”are used interchangeably throughout this document. Likewise, the terms“functional group,” “group,” and “substituent” are also usedinterchangeably in this document. For purposes of this disclosure,“hydrocarbyl radical” is defined to be C₁ to C₂₀ radicals, that may belinear, branched, or cyclic (aromatic or non-aromatic); and may includesubstituted hydrocarbyl radicals as defined herein. In an embodiment, afunctional group may comprise a hydrocarbyl radical, a substitutedhydrocarbyl radical, or a combination thereof.

Substituted hydrocarbyl radicals are radicals in which at least onehydrogen atom has been substituted with a heteroatom or heteroatomcontaining group, or with atoms from Groups 13, 14, 15, 16, and 17 ofthe Periodic Table of Elements, or a combination thereof, or with atleast one functional group, such as halogen (Cl, Br, I, F), NR*₂, OR*,SeR*, TeR*, PR*₂, AsR*₂, SbR*₂, SR*, BR*₂, SiR*₃, GeR*₃, SnR*₃, PbR*₃,and the like or where at least one heteroatom has been inserted withinthe hydrocarbyl radical, such as halogen (Cl, Br, I, F), O, S, Se, Te,NR*, PR*, AsR*, SbR*, BR*, SiR*₂, GeR*₂, SnR*₂, PbR*₂, and the like,where R* is, independently, hydrogen or a hydrocarbyl radical, or anycombination thereof.

In an embodiment, the hydrocarbyl radical is independently selected frommethyl, ethyl, ethenyl, and isomers of propyl, butyl, pentyl, hexyl,heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl,pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl,heneicosyl, docosyl, tricosyl, tetracosyl, pentacosyl, hexacosyl,heptacosyl, octacosyl, nonacosyl, triacontyl, propenyl, butenyl,pentenyl, hexenyl, heptenyl, octenyl, nonenyl, decenyl, undecenyl,dodecenyl, tridecenyl, tetradecenyl, pentadecenyl, hexadecenyl,heptadecenyl, octadecenyl, nonadecenyl, eicosenyl, heneicosenyl,docosenyl, tricosenyl, tetracosenyl, pentacosenyl, hexacosenyl,heptacosenyl, octacosenyl, nonacosenyl, triacontenyl, propynyl, butynyl,pentynyl, hexynyl, heptynyl, octynyl, nonynyl, decynyl, undecynyl,dodecynyl, tridecynyl, tetradecynyl, pentadecynyl, hexadecynyl,heptadecynyl, octadecynyl, nonadecynyl, eicosynyl, heneicosynyl,docosynyl, tricosynyl, tetracosynyl, pentacosynyl, hexacosynyl,heptacosynyl, octacosynyl, nonacosynyl, and triacontynyl. Also includedare isomers of saturated, partially unsaturated, and aromatic cyclicstructures wherein the radical may additionally be subjected to thetypes of substitutions described above. Examples include phenyl,methylphenyl, benzyl, methylbenzyl, naphthyl, cyclohexyl, cyclohexenyl,methylcyclohexyl, and the like. For this disclosure, when a radical islisted, it indicates that radical type and all other radicals formedwhen that radical type is subjected to the substitutions defined above.Alkyl, alkenyl, and alkynyl radicals listed include all isomersincluding, where appropriate, cyclic isomers, for example, butylincludes n-butyl, 2-methylpropyl, 1-methylpropyl, tert-butyl, andcyclobutyl (and analogous substituted cyclopropyls); pentyl includesn-pentyl, cyclopentyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl,1-ethylpropyl, and neopentyl (analogous substituted cyclobutyls andcyclopropyls); and butenyl includes E and Z forms of 1-butenyl,2-butenyl, 3-butenyl, 1-methyl-1-propenyl, 1-methyl-2-propenyl,2-methyl-1-propenyl, and 2-methyl-2-propenyl (cyclobutenyls andcyclopropenyls). Cyclic compounds having substitutions include allisomer forms, for example, methylphenyl would includeortho-methylphenyl, meta-methylphenyl, and para-methylphenyl;dimethylphenyl would include 2,3-dimethylphenyl, 2,4-dimethylphenyl,2,5-dimethylphenyl, 2,6-diphenylmethyl, 3,4-dimethylphenyl, and3,5-dimethylphenyl.

An “olefin,” alternatively referred to as “alkene,” is a linear,branched, or cyclic compound of carbon and hydrogen having at least onedouble bond. For purposes of this specification and the claims appendedthereto, when a polymer or copolymer is referred to as comprising anolefin, including, but not limited to, ethylene, propylene, and butene,the olefin present in such polymer or copolymer is the polymerized formof the olefin. For example, when a copolymer is said to have an“ethylene” content of 35 wt % to 55 wt %, it is understood that the merunit in the copolymer is derived from ethylene in the polymerizationreaction and said derived units are present at 35 wt % to 55 wt %, basedupon the weight of the copolymer. A “polymer” has two or more of thesame or different mer units. A “homopolymer” is a polymer having merunits that are the same. A “copolymer” is a polymer having two or moremer units that are different from each other. A “terpolymer” is apolymer having three mer units that are different from each other.“Different” as used to refer to mer units indicates that the mer unitsdiffer from each other by at least one atom or are differentisomerically. Accordingly, the definition of copolymer, as used herein,includes terpolymers and the like. An oligomer is a polymer having a lowmolecular weight. In some embodiments, an oligomer has an Mn of 21,000g/mol or less (e.g., 2,500 g/mol or less); in other embodiments, anoligomer has a low number of mer units (such as 75 mer units or less).

An “alpha-olefin” is an olefin having a double bond at the alpha (or 1-)position. A “linear alpha-olefin” or “LAO” is an olefin with a doublebond at the alpha position and a linear hydrocarbon chain. A“polyalphaolefin” or “PAO” is a polymer having two or more alpha-olefinunits. For the purposes of this disclosure, the term “α-olefin” includesC₂-C₂₀ olefins. Non-limiting examples of α-olefins include ethylene,propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene,1-decene, 1-undecene 1-dodecene, 1-tridecene, 1-tetradecene,1-pentadecene, 1-hexadecene, 1-heptadecene, 1-octadecene, 1-nonadecene,1-eicosene, 1-heneicosene, 1-docosene, 1-tricosene, 1-tetracosene,1-pentacosene, 1-hexacosene, 1-heptacosene, 1-octacosene, 1-nonacosene,1-triacontene, 4-methyl-1-pentene, 3-methyl-1-pentene,5-methyl-1-nonene, 3,5,5-trimethyl-1-hexene, vinylcyclohexane, andvinylnorbornane. Non-limiting examples of cyclic olefins and diolefinsinclude cyclopropene, cyclobutene, cyclopentene, cyclohexene,cycloheptene, cyclooctene, cyclononene, cyclodecene, norbornene,4-methylnorbornene, 2-methylcyclopentene, 4-methylcyclopentene,vinylcyclohexane, norbornadiene, dicyclopentadiene,5-ethylidene-2-norbornene, vinylcyclohexene, 5-vinyl-2-norbornene,1,3-divinylcyclopentane, 1,2-divinylcyclohexane, 1,3-divinylcyclohexane,1,4-divinylcyclohexane, 1,5-divinylcyclooctane,1-allyl-4-vinylcyclohexane, 1,4-diallylcyclohexane,1-allyl-5-vinylcyclooctane, and 1,5-diallylcyclooctane.

For purposes herein, a polymer or polymeric chain comprises aconcatenation of carbon atoms bonded to each other in a linear or abranched chain, which is referred to herein as the backbone of thepolymer (e.g., polyethylene). The polymeric chain may further comprisevarious pendent groups attached to the polymer backbone which werepresent on the monomers from which the polymer was produced. Thesependent groups are not to be confused with branching of the polymerbackbone, the difference between pendent side chains and both short andlong chain branching being readily understood by one of skill in theart.

The terms “catalyst” and “catalyst compound” are defined to mean acompound capable of initiating catalysis. In the description herein, thecatalyst may be described as a catalyst precursor, a pre-catalystcompound, or a transition metal compound (for example, a metallocenecompound), and these terms are used interchangeably. A catalyst compoundmay be used by itself to initiate catalysis or may be used incombination with an activator to initiate catalysis. When the catalystcompound is combined with an activator to initiate catalysis, thecatalyst compound is often referred to as a pre-catalyst or catalystprecursor. A “catalyst system” is a combination of at least one catalystcompound, an optional activator, an optional co-activator, and anoptional support material, where the system can polymerize monomers topolymer. For the purposes of this invention and the claims thereto, whencatalyst systems are described as comprising neutral stable forms of thecomponents, it is well understood by one of ordinary skill in the art,that the ionic form of the component is the form that reacts with themonomers to produce polymers.

An “anionic ligand” is a negatively charged ligand which donates one ormore pairs of electrons to a metal ion. A “neutral donor ligand” is aneutrally charged ligand which donates one or more pairs of electrons toa metal ion.

A “scavenger” is a compound that is typically added to facilitatepolymerization by scavenging impurities. Some scavengers may also act asactivators and may be referred to as co-activators. A co-activator, thatis not a scavenger, may also be used in conjunction with an activator inorder to form an active catalyst. In some embodiments, a co-activatorcan be pre-mixed with the catalyst compound to form an alkylatedcatalyst compound, also referred to as an alkylated invention compound.

A propylene polymer is a polymer having at least 50 mol % of propylene.As used herein, Mn is number average molecular weight as determined byproton nuclear magnetic resonance spectroscopy (¹H NMR) where the datais collected at 120° C. in a 5 mm probe using a spectrometer with a ¹Hfrequency of at least 400 MHz. Data is recorded using a maximum pulsewidth of 45°, 8 seconds between pulses and signal averaging 120transients. Unless stated otherwise, Mw is weight average molecularweight as determined by gel permeation chromatography (GPC), Mz is zaverage molecular weight as determined by GPC as described in the VINYLTERMINATED MACROMONOMERS section below, wt % is weight percent, and mol% is mole percent. Molecular weight distribution (MWD) is defined to beMw (GPC) divided by Mn (GPC). Unless otherwise noted, all molecularweight units, e.g., Mw, Mn, Mz, are g/mol.

The following abbreviations may be used through this specification: Meis methyl, Ph is phenyl, Et is ethyl, Pr is propyl, iPr is isopropyl,n-Pr is normal propyl, Bu is butyl, iBu is isobutyl, tBu is tertiarybutyl, p-tBu is para-tertiary butyl, nBu is normal butyl, TMS istrimethylsilyl, TIBAL is triisobutylaluminum, TNOAL is triisobutyln-octylaluminum, MAO is methylalumoxane, pMe is para-methyl, Ar* is2,6-diisopropylaryl, Bz is benzyl, THF is tetrahydrofuran.

In one aspect, this invention relates to a polyolefin compositioncomprising one or more of the following formulae:

wherein the PO is the residual portion of a vinyl terminatedmacromonomer (VTM) having had a terminal unsaturated carbon of anallylic chain and a vinyl carbon adjacent to the terminal unsaturatedcarbon;X is attached to the terminal portion of the VTM to provide PO—X or atthe vinylidene carbon of the VTM to provide PO—CHXCH₃; and

X is Cl, Br, I, or F.

In another embodiment this invention relates to a polyolefin compositioncomprising one or more of the following formulae:

wherein the PO is the residual portion of a vinyl terminatedmacromonomer (VTM, preferably any of those described herein) having hada terminal unsaturated carbon of an allylic chain and a vinyl carbonadjacent to the terminal unsaturated carbon;Y is a hydroxyl, an ether group, a cyano, a C₁-C₂₀ alkyl group, acyclopentadienyl, an aromatic group, or a phthalimide group. In apreferred embodiment, the ether group comprises the formula:

—OR₁—O—R₂_(n)R₉,

wherein R₁ is an alkyl or an aryl; R₂ is a bond, an alkyl or an aryl; R₉is an alkyl or an aryl;and n is from 1 to about 500, preferably the ether group comprises theformula:

—OR₁—O—R₄_(n)OR₈,

wherein each R₁ and R₄ is, independently, an alkyl or an aryl;R₈ is an alkyl or an aryl; andn is from 1 to about 500.

In another embodiment, this invention relates to a method tofunctionalize a vinyl terminated macromonomer (VTM as described herein)comprising the step: contacting a VTM with a compound having the formulaHX, wherein X is Cl, I, Br, or F to provide an X functionalized VTM. Ina preferred embodiment, the method further comprising the step ofcontacting the X functionalized VTM with a hydroxyl, an alkoxide, anaryl anion, a carbanion, a cyano or a phthalimide group. In a preferredembodiment, the alcohol group for the alkoxide comprises the formula:

HOR₁—O—R₂_(n)R₉,

wherein R₁ is an alkyl or an aryl; R₂ is a bond, an alkyl or an aryl; R₉is an alkyl or an aryl; and n is from 1 to about 500, preferably thealcohol group for the alkoxide comprises the formula:

HOR₁—O—R₄_(n)OR₈,

wherein each R₁ and R₄ is, independently, an alkyl or an aryl; R₈ is, analkyl or an aryl; and is from 1 to about 500.

In a preferred embodiment, the method described above provides a 90%yield.

In a preferred embodiment, the M_(w)/M_(n) of the VTM and/or Xfunctionalized VTM is from 2 to 4, preferably from 1.1 to 1.02.

Vinyl Terminated Macromonomers

A “vinyl terminated macromonomer,” (also referred to as a “vinylterminated polyolefin”) as used herein, refers to one or more of:

(i) a vinyl terminated polymer having at least 5% allyl chain ends(preferably 15%, 20%, 30%, 40%, 50%, 60%, 70%, 80%, 90%, 95%, 98%, or99%);(ii) a vinyl terminated polymer having an Mn of at least 160 g/mol,preferably at least 200 g/mol (measured by ¹H NMR) comprising of one ormore C₄ to C₄₀ higher olefin derived units, where the higher olefinpolymer comprises substantially no propylene derived units; and whereinthe higher olefin polymer has at least 5% allyl chain ends;(iii) a copolymer having an Mn of 300 g/mol or more (measured by ¹H NMR)comprising (a) from about 20 mol % to about 99.9 mol % of at least oneC₅ to C₄₀ higher olefin, and (b) from about 0.1 mol % to about 80 mol %of propylene, wherein the higher olefin copolymer has at least 40% allylchain ends;(iv) a copolymer having an Mn of 300 g/mol or more (measured by ¹H NMR),and comprises (a) from about 80 mol % to about 99.9 mol % of at leastone C₄ olefin, (b) from about 0.1 mol % to about 20 mol % of propylene;and wherein the vinyl terminated macromonomer has at least 40% allylchain ends relative to total unsaturation;(v) a co-oligomer having an Mn of 300 g/mol to 30,000 g/mol (measured by¹H NMR) comprising 10 mol % to 90 mol % propylene and 10 mol % to 90 mol% of ethylene, wherein the oligomer has at least X % allyl chain ends(relative to total unsaturations), where: 1) X=(−0.94*(mol % ethyleneincorporated)+100), when 10 mol % to 60 mol % ethylene is present in theco-oligomer, 2) X=45, when greater than 60 mol % and less than 70 mol %ethylene is present in the co-oligomer, and 3) X=(1.83*(mol % ethyleneincorporated)−83), when 70 mol % to 90 mol % ethylene is present in theco-oligomer;(vi) a propylene oligomer, comprising more than 90 mol % propylene andless than 10 mol % ethylene wherein the oligomer has: at least 93% allylchain ends, a number average molecular weight (Mn) of about 500 g/mol toabout 20,000 g/mol, an isobutyl chain end to allylic vinyl group ratioof 0.8:1 to 1.35:1.0, less than 100 ppm aluminum, and/or less than 250regio defects per 10,000 monomer units;(vii) a propylene oligomer, comprising: at least 50 mol % propylene andfrom 10 mol % to 50 mol % ethylene, wherein the oligomer has: at least90% allyl chain ends, an Mn of about 150 g/mol to about 20,000 g/mol,preferably 10,000 g/mol, and an isobutyl chain end to allylic vinylgroup ratio of 0.8:1 to 1.2:1.0, wherein monomers having four or morecarbon atoms are present at from 0 mol % to 3 mol %;(viii) a propylene oligomer, comprising: at least 50 mol % propylene,from 0.1 mol % to 45 mol % ethylene, and from 0.1 mol % to 5 mol % C₄ toC₁₂ olefin, wherein the oligomer has: at least 90% allyl chain ends, anMn of about 150 g/mol to about 10,000 g/mol, and an isobutyl chain endto allylic vinyl group ratio of 0.8:1 to 1.35:1.0;(ix) a propylene oligomer, comprising: at least 50 mol % propylene, from0.1 mol % to 45 mol % ethylene, and from 0.1 mol % to 5 mol % diene,wherein the oligomer has: at least 90% allyl chain ends, an Mn of about150 g/mol to about 10,000 g/mol, and an isobutyl chain end to allylicvinyl group ratio of 0.7:1 to 1.35:1.0;(x) a homo-oligomer, comprising propylene, wherein the oligomer has: atleast 93% allyl chain ends, an Mn of about 500 g/mol to about 70,000g/mol, alternately to about 20,000 g/mol, an isobutyl chain end toallylic vinyl group ratio of 0.8:1 to 1.2:1.0, and less than 1400 ppmaluminum;(xi) vinyl terminated polyethylene having: (a) at least 60% allyl chainends; (b) a molecular weight distribution of less than or equal to 4.0;(c) a g′(vis) of greater than 0.95; and (d) an Mn (¹H NMR) of at least20,000 g/mol; and(xii) vinyl terminated polyethylene having: (a) at least 50% allyl chainends; (b) a molecular weight distribution of less than or equal to 4.0;(c) a g′(vis) of 0.95 or less; (d) an Mn (¹H NMR) of at least 7,000g/mol; and (e) a Mn (GPC)/Mn (¹H NMR) in the range of from about 0.8 toabout 1.2.

It is understood by those of ordinary skill in the art that when theVTM's, as described here, are reacted with another material the “vinyl”(e.g. the allyl chain end) is involved in the reaction and has beentransformed. Thus, the language used herein describing that a fragmentof the final product (typically referred to as PO in the formulaeherein) is the residual portion of a vinyl terminated macromonomer (VTM)having had a terminal unsaturated carbon of an allylic chain and a vinylcarbon adjacent to the terminal unsaturated carbon, is meant to refer tothe fact that the VTM has been incorporated in the product. Similarlystating that a product or material comprises a VTM means that thereacted form of the VTM is present, unless the context clearly indicatesotherwise (such as a mixture of ingredients that do not have a catalyticagent present.)

In some embodiments, the vinyl terminated macromonomer has an Mn of atleast 200 g/mol, (e.g., 200 g/mol to 100,000 g/mol, e.g., 200 g/mol to75,000 g/mol, e.g., 200 g/mol to 60,000 g/mol, e.g., 300 g/mol to 60,000g/mol, or e.g., 750 g/mol to 30,000 g/mol) (measured by ¹H NMR) andcomprises one or more (e.g., two or more, three or more, four or more,and the like) C₄ to C₄₀ (e.g., C₄ to C₃₀, C₄ to C₂₀, or C₄ to C₁₂, e.g.,butene, pentene, hexene, heptene, octene, nonene, decene, undecene,dodecene, norbornene, norbornadiene, dicyclopentadiene, cyclopentene,cycloheptene, cyclooctene, cyclooctadiene, cyclododecene,7-oxanorbornene, 7-oxanorbornadiene, substituted derivatives thereof,and isomers thereof) olefin derived units, where the vinyl terminatedmacromonomer comprises substantially no propylene derived units (e.g.,less than 0.1 wt % propylene, e.g., 0 wt %); and wherein the vinylterminated macromonomer has at least 5% (at least 10%, at least 15%, atleast 20%, at least 30%, at least 40%, at least 50%, at least 60%, atleast 70%; at least 80%, at least 90%, or at least 95%) allyl chain ends(relative to total unsaturation); and optionally, an allyl chain end tovinylidene chain end ratio of 1:1 or greater (e.g., greater than 2:1,greater than 2.5:1, greater than 3:1, greater than 5:1, or greater than10:1); and even further optionally, e.g., substantially no isobutylchain ends (e.g., less than 0.1 wt % isobutyl chain ends). In someembodiments, the vinyl terminated macromonomers may also compriseethylene derived units, e.g., at least 5 mol % ethylene (e.g., at least15 mol % ethylene, e.g., at least 25 mol % ethylene, e.g., at least 35mol % ethylene, e.g., at least 45 mol % ethylene, e.g., at least 60 mol% ethylene, e.g., at least 75 mol % ethylene, or e.g., at least 90 mol %ethylene). Such vinyl terminated macromonomers are further described inU.S. Pat. No. 8,426,659, which is hereby incorporated by reference.

In some embodiments, the vinyl terminated macromonomers may have an Mn(measured by ¹H NMR) of greater than 200 g/mol (e.g., 300 g/mol to60,000 g/mol, 400 g/mol to 50,000 g/mol, 500 g/mol to 35,000 g/mol, 300g/mol to 15,000 g/mol, 400 g/mol to 12,000 g/mol, or 750 g/mol to 10,000g/mol), and comprise:

(a) from about 20 mol % to 99.9 mol % (e.g., from about 25 mol % toabout 90 mol %, from about 30 mol % to about 85 mol %, from about 35 mol% to about 80 mol %, from about 40 mol % to about 75 mol %, or fromabout 50 mol % to about 95 mol %) of at least one C₅ to C₄₀ (e.g., C₆ toC₂₀) higher olefin; and(b) from about 0.1 mol % to 80 mol % (e.g., from about 5 mol % to 70 mol%, from about 10 mol % to about 65 mol %, from about 15 mol % to about55 mol %, from about 25 mol % to about 50 mol %, or from about 30 mol %to about 80 mol %) of propylene;wherein the vinyl terminated macromonomer has at least 40% allyl chainends (e.g., at least 50% allyl chain ends, at least 60% allyl chainends, at least 70% allyl chain ends, or at least 80% allyl chain ends,at least 90% allyl chain ends, at least 95% allyl chain ends) relativeto total unsaturation; and, optionally, an isobutyl chain end to allylchain end ratio of less than 0.70:1, less than 0.65:1, less than 0.60:1,less than 0.50:1, or less than 0.25:1; and further optionally, an allylchain end to vinylidene chain end ratio of greater than 2:1 (e.g.,greater than 2.5:1, greater than 3:1, greater than 5:1, or greater than10:1); and even further optionally, an allyl chain end to vinylene ratiois greater than 1:1 (e.g., greater than 2:1 or greater than 5:1). Suchmacromonomers are further described in U.S. Pat. No. 8,399,724, herebyincorporated by reference.

In another embodiment, the vinyl terminated macromonomer has an Mn of300 g/mol or more (measured by ¹H NMR, e.g., 300 g/mol to 60,000 g/mol,400 g/mol to 50,000 g/mol, 500 g/mol to 35,000 g/mol, 300 g/mol to15,000 g/mol, 400 g/mol to 12,000 g/mol, or 750 g/mol to 10,000 g/mol),and comprises:

(a) from about 80 mol % to about 99.9 mol % of at least one C₄ olefin,e.g., about 85 mol % to about 99.9 mol %, e.g., about 90 mol % to about99.9 mol %;(b) from about 0.1 mol % to about 20 mol % of propylene, e.g., about 0.1mol % to about 15 mol %, e.g., about 0.1 mol % to about 10 mol %; andwherein the vinyl terminated macromonomer has at least 40% allyl chainends (e.g., at least 50% allyl chain ends, at least 60% allyl chainends, at least 70% allyl chain ends, or at least 80% allyl chain ends,at least 90% allyl chain ends, at least 95% allyl chain ends) relativeto total unsaturation, and in some embodiments, an isobutyl chain end toallyl chain end ratio of less than 0.70:1, less than 0.65:1, less than0.60:1, less than 0.50:1, or less than 0.25:1, and in furtherembodiments, an allyl chain end to vinylidene group ratio of more than2:1, more than 2.5:1, more than 3:1, more than 5:1, or more than 10:1.Such macromonomers are also further described in U.S. Pat. No.8,399,724, which is hereby incorporated by reference.

In other embodiments, the vinyl terminated macromonomer is a propyleneco-oligomer having an Mn of 300 g/mol to 30,000 g/mol as measured by ¹HNMR (e.g., 400 g/mol to 20,000 g/mol, e.g., 500 g/mol to 15,000 g/mol,e.g., 600 g/mol to 12,000 g/mol, e.g., 800 g/mol to 10,000 g/mol, e.g.,900 g/mol to 8,000 g/mol, e.g., 900 g/mol to 7,000 g/mol), comprising 10mol % to 90 mol % propylene (e.g., 15 mol % to 85 mol %, e.g., 20 mol %to 80 mol %, e.g., 30 mol % to 75 mol %, e.g., 50 mol % to 90 mol %) and10 mol % to 90 mol % (e.g., 85 mol % to 15 mol %, e.g., 20 mol % to 80mol %, e.g., 25 mol % to 70 mol %, e.g., 10 mol % to 50 mol %) of one ormore alpha-olefin comonomers (e.g., ethylene, butene, hexene, or octene,e.g., ethylene), wherein the oligomer has at least X % allyl chain ends(relative to total unsaturations), where: 1) X=(−0.94 (mol % ethyleneincorporated)+100{alternately 1.20 (−0.94 (mol % ethyleneincorporated)+100), alternately 1.50(−0.94 (mol % ethyleneincorporated)+100)}), when 10 mol % to 60 mol % ethylene is present inthe co-oligomer; 2) X=45 (alternately 50, alternately 60), when greaterthan 60 mol % and less than 70 mol % ethylene is present in theco-oligomer; and 3) X=(1.83*(mol % ethylene incorporated)−83,{alternately 1.20 [1.83*(mol % ethylene incorporated)-83], alternately1.50 [1.83*(mol % ethylene incorporated)−83]}), when 70 mol % to 90 mol% ethylene is present in the co-oligomer. Such macromonomers are furtherdescribed in U.S. Pat. No. 8,372,930, which is hereby incorporated byreference.

In other embodiments, the vinyl terminated macromonomer is a propyleneoligomer, comprising more than 90 mol % propylene (e.g., 95 mol % to 99mol %, e.g., 98 mol % to 9 mol %) and less than 10 mol % ethylene (e.g.,1 mol % to 4 mol %, e.g., 1 mol % to 2 mol %), wherein the oligomer has:at least 93% allyl chain ends (e.g., at least 95%, e.g., at least 97%,e.g., at least 98%); a number average molecular weight (Mn) of about 400g/mol to about 30,000 g/mol, as measured by ¹H NMR (e.g., 500 g/mol to20,000 g/mol, e.g., 600 g/mol to 15,000 g/mol, e.g., 700 g/mol to 10,000g/mol, e.g., 800 g/mol to 9,000 g/mol, e.g., 900 g/mol to 8,000 g/mol,e.g., 1,000 g/mol to 6,000 g/mol); an isobutyl chain end to allylicvinyl group ratio of 0.8:1 to 1.35:1.0, and less than 1400 ppm aluminum,(e.g., less than 1200 ppm, e.g., less than 1000 ppm, e.g., less than 500ppm, e.g., less than 100 ppm). Such macromonomers are further describedin U.S. Pat. No. 8,372,930.

In other embodiments, the vinyl terminated macromonomer is a propyleneoligomer, comprising: at least 50 mol % (e.g., 60 mol % to 90 mol %,e.g., 70 mol % to 90 mol %) propylene and from 10 mol % to 50 mol %(e.g., 10 mol % to 40 mol %, e.g., 10 mol % to 30 mol %) ethylene,wherein the oligomer has: at least 90% allyl chain ends (e.g., at least91%, e.g., at least 93%, e.g., at least 95%, e.g., at least 98%); an Mnof about 150 g/mol to about 20,000 g/mol, as measured by ¹H NMR (e.g.,200 g/mol to 15,000 g/mol, e.g., 250 g/mol to 15,000 g/mol, e.g., 300g/mol to 10,000 g/mol, e.g., 400 g/mol to 9,500 g/mol, e.g., 500 g/molto 9,000 g/mol, e.g., 750 g/mol to 9,000 g/mol); and an isobutyl chainend to allylic vinyl group ratio of 0.8:1 to 1.3:1.0, wherein monomershaving four or more carbon atoms are present at from 0 mol % to 3 mol %(e.g., at less than 1 mol %, e.g., less than 0.5 mol %, e.g., at 0 mol%). Such macromonomers are further described in U.S. Pat. No. 8,372,930.

In other embodiments, the vinyl terminated macromonomer is a propyleneoligomer, comprising: at least 50 mol % (e.g., at least 60 mol %, e.g.,70 mol % to 99.5 mol %, e.g., 80 mol % to 99 mol %, e.g., 90 mol % to98.5 mol %) propylene, from 0.1 mol % to 45 mol % (e.g., at least 35 mol%, e.g., 0.5 mol % to 30 mol %, e.g., 1 mol % to 20 mol %, e.g., 1.5 mol% to 10 mol %) ethylene, and from 0.1 mol % to 5 mol % (e.g., 0.5 mol %to 3 mol %, e.g., 0.5 mol % to 1 mol %) C₄ to C₁₂ olefin (such asbutene, hexene, or octene, e.g., butene), wherein the oligomer has: atleast 90% allyl chain ends (e.g., at least 91%, e.g., at least 93%,e.g., at least 95%, e.g., at least 98%); a number average molecularweight (Mn) of about 150 g/mol to about 15,000 g/mol, as measured by ¹HNMR (e.g., 200 g/mol to 12,000 g/mol, e.g., 250 g/mol to 10,000 g/mol,e.g., 300 g/mol to 10,000 g/mol, e.g., 400 g/mol to 9500 g/mol, e.g.,500 g/mol to 9,000 g/mol, e.g., 750 g/mol to 9,000 g/mol); and anisobutyl chain end to allylic vinyl group ratio of 0.8:1 to 1.35:1.0.Such macromonomers are further described in U.S. Pat. No. 8,372,930.

In other embodiments, the vinyl terminated macromonomer is a propyleneoligomer, comprising: at least 50 mol % (e.g., at least 60 mol %, e.g.,70 mol % to 99.5 mol %, e.g., 80 mol % to 99 mol %, e.g., 90 mol % to98.5 mol %) propylene, from 0.1 mol % to 45 mol % (e.g., at least 35 mol%, e.g., 0.5 mol % to 30 mol %, e.g., 1 mol % to 20 mol %, e.g., 1.5 mol% to 10 mol %) ethylene, and from 0.1 mol % to 5 mol % (e.g., 0.5 mol %to 3 mol %, e.g., 0.5 mol % to 1 mol %) diene (such as C₄ to C₁₂alpha-omega dienes (such as butadiene, hexadiene, octadiene),norbornene, ethylidene norbornene, vinylnorbornene, norbornadiene, anddicyclopentadiene), wherein the oligomer has at least 90% allyl chainends (e.g., at least 91%, e.g., at least 93%, e.g., at least 95%, e.g.,at least 98%); a number average molecular weight (Mn) of about 150 g/molto about 20,000 g/mol, as measured by ¹H NMR (e.g., 200 g/mol to 15,000g/mol, e.g., 250 g/mol to 12,000 g/mol, e.g., 300 g/mol to 10,000 g/mol,e.g., 400 g/mol to 9,500 g/mol, e.g., 500 g/mol to 9,000 g/mol, e.g.,750 g/mol to 9,000 g/mol); and an isobutyl chain end to allylic vinylgroup ratio of 0.7:1 to 1.35:1.0. Such macromonomers are furtherdescribed in U.S. Pat. No. 8,372,930.

In other embodiments, the vinyl terminated macromonomer is a propylenehomo-oligomer, comprising propylene and less than 0.5 wt % comonomer,e.g., 0 wt % comonomer, wherein the oligomer has:

i) at least 93% allyl chain ends (e.g., at least 95%, e.g., at least96%, e.g., at least 97%, e.g., at least 98%, e.g., at least 99%);ii) a number average molecular weight (Mn) of about 500 g/mol to about20,000 g/mol, as measured by ¹H NMR (e.g., 500 g/mol to 15,000 g/mol,e.g., 700 g/mol to 10,000 g/mol, e.g., 800 g/mol to 8,000 g/mol, e.g.,900 g/mol to 7,000 g/mol, e.g., 1,000 g/mol to 6,000 g/mol, e.g., 1,000g/mol to 5,000 g/mol);iii) an isobutyl chain end to allylic vinyl group ratio of 0.8:1 to1.3:1.0; andiv) less than 1400 ppm aluminum, (e.g., less than 1200 ppm, e.g., lessthan 1000 ppm, e.g., less than 500 ppm, e.g., less than 100 ppm). Suchmacromonomers are also further described in U.S. Pat. No. 8,372,930.

The vinyl terminated macromonomers may be homopolymers, copolymers,terpolymers, and so on. Any vinyl terminated macromonomers describedherein has one or more of:

(i) an isobutyl chain end to allylic vinyl group ratio of 0.8:1 to1.3:1.0;(ii) an allyl chain end to vinylidene chain end ratio of greater than2:1 (e.g., greater than 2.5:1, greater than 3:1, greater than 5:1, orgreater than 10:1);(iii) an allyl chain end to vinylene ratio is greater than 1:1 (e.g.,greater than 2:1 or greater than 5:1); and(iv) at least 5% allyl chain ends (preferably 15%, 20%, 30%, 40%, 50%,60%, 70%, 80%, 90%, 95%, 98%, or 99%).

Vinyl terminated macromonomers generally have a saturated chain end (orterminus) and/or an unsaturated chain end or terminus. The unsaturatedchain end of the vinyl terminated macromonomer comprises an “allyl chainend” or a “3-alkyl” chain end. An allyl chain end is represented byCH₂CH—CH₂₋, as shown in the formula:

where M represents the polymer chain. “Allylic vinyl group,” “allylchain end,” “vinyl chain end,” “vinyl termination,” “allylic vinylgroup,” and “vinyl terminated” are used interchangeably in the followingdescription. The number of allyl chain ends, vinylidene chain ends,vinylene chain ends, and other unsaturated chain ends is determinedusing ¹H NMR at 120° C. using deuterated tetrachloroethane as thesolvent on an at least 250 MHz NMR spectrometer, and in selected cases,confirmed by ¹³C NMR. Resconi has reported proton and carbon assignments(neat perdeuterated tetrachloroethane used for proton spectra, while a50:50 mixture of normal and perdeuterated tetrachloroethane was used forcarbon spectra; all spectra were recorded at 100° C. on a BRUKERspectrometer operating at 500 MHz for proton and 125 MHz for carbon) forvinyl terminated oligomers in J. American Chemical Soc., 114, 1992, pp.1025-1032 that are useful herein. Allyl chain ends are reported as amolar percentage of the total number of moles of unsaturated groups(that is, the sum of allyl chain ends, vinylidene chain ends, vinylenechain ends, and the like).

A 3-alkyl chain end (where the alkyl is a C₁ to C₃₈ alkyl), alsoreferred to as a “3-alkyl vinyl end group” or a “3-alkyl vinyltermination,” is represented by the formula:

where “••••” represents the polyolefin chain and R^(b) is a C₁ to C₃₈alkyl group, or a C₁ to C₂₀ alkyl group, such as methyl, ethyl, propyl,butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, andthe like. The amount of 3-alkyl chain ends is determined using ¹³C NMRas set out below.

¹³C NMR data is collected at 120° C. at a frequency of at least 100 MHz,using a BRUKER 400 MHz NMR spectrometer. A 90 degree pulse, anacquisition time adjusted to give a digital resolution between 0.1 and0.12 Hz, at least a 10 second pulse acquisition delay time withcontinuous broadband proton decoupling using swept square wavemodulation without gating is employed during the entire acquisitionperiod. The spectra is acquired with time averaging to provide a signalto noise level adequate to measure the signals of interest. Samples aredissolved in tetrachloroethane-d₂ at concentrations between 10 wt % to15 wt % prior to being inserted into the spectrometer magnet. Prior todata analysis spectra are referenced by setting the chemical shift ofthe TCE solvent signal to 74.39 ppm. Chain ends for quantization wereidentified using the signals shown in the table below. N-butyl andn-propyl were not reported due to their low abundance (less than 5%)relative to the chain ends shown in the table below.

Chain End ¹³C NMR Chemical Shift P~i-Bu 23-5 to 25.5 and 25.8 to 26.3ppm E~i-Bu 39.5 to 40.2 ppm P~Vinyl 41.5 to 43 ppm E~Vinyl 33.9 to 34.4ppm

The “allyl chain end to vinylidene chain end ratio” is defined to be theratio of the percentage of allyl chain ends to the percentage ofvinylidene chain ends. The “allyl chain end to vinylene chain end ratio”is defined to be the ratio of the percentage of allyl chain ends to thepercentage of vinylene chain ends. Vinyl terminated macromonomerstypically also have a saturated chain end. In polymerizations wherepropylene is present, the polymer chain may initiate growth in apropylene monomer, thereby generating an isobutyl chain end. An“isobutyl chain end” is defined to be an end or terminus of a polymer,represented as shown in the formula below:

where M represents the polymer chain. Isobutyl chain ends are determinedaccording to the procedure set out in WO 2009/155471. The “isobutylchain end to allylic vinyl group ratio” is defined to be the ratio ofthe percentage of isobutyl chain ends to the percentage of allyl chainends. The “isobutyl chain end to alpha bromo carbon ratio” is defined tobe the ratio of the percentage of isobutyl chain ends to the percentageof brominated chain ends (at about 34 ppm).

In polymerizations comprising C₄ or greater monomers (or “higher olefin”monomers), the saturated chain end may be a C₄ or greater (or “higherolefin”) chain end, as shown in the formula below:

where M represents the polymer chain and n is an integer selected from 4to 40. This is especially true when there is substantially no ethyleneor propylene in the polymerization. In an ethylene/(C₄ or greatermonomer) copolymerization, the polymer chain may initiate growth in anethylene monomer, thereby generating a saturated chain end which is anethyl chain end. Mn (¹H NMR) is determined according to the followingNMR method. ¹H NMR data is collected at either 25° C. or 120° C. (forpurposes of the claims, 120° C. shall be used) in a 5 mm probe using aVarian spectrometer with a ¹H frequency of 250 MHz, 400 MHz, or 500 MHz(for the purpose of the claims, a proton frequency of 400 MHz is used).Data are recorded using a maximum pulse width of 45°, 8 seconds betweenpulses and signal averaging 120 transients. Spectral signals areintegrated and the number of unsaturation types per 1000 carbons iscalculated by multiplying the different groups by 1000 and dividing theresult by the total number of carbons. Mn is calculated by dividing thetotal number of unsaturated species into 14,000, and has units of g/mol.The chemical shift regions for the olefin types are defined to bebetween the following spectral regions.

Unsaturation Type Region (ppm) Number of hydrogens per structure Vinyl4.95-5.10 2 Vinylidene (VYD) 4.70-4.84 2 Vinylene 5.31-5.55 2Trisubstituted 5.11-5.30 1

Unless otherwise stated, Mn (GPC) is determined using the GPC-DRI methoddescribed below, however, Nota Bene: for the purpose of the claims, Mnis determined by ¹H NMR. Mn, Mw, and Mz may be measured by using a GelPermeation Chromatography (GPC) method using a High Temperature SizeExclusion Chromatograph (SEC, either from Waters Corporation or PolymerLaboratories), equipped with a differential refractive index detector(DRI). Molecular weight distribution (MWD) is Mw (GPC)/Mn (GPC).Experimental details, are described in: T. Sun, P. Brant, R. R. Chance,and W. W. Graessley, Macromolecules, Volume 34, Number 19, pp.6812-6820, (2001) and references therein. Three Polymer LaboratoriesPLgel 10 mm Mixed-B columns are used. The nominal flow rate is 0.5cm³/min and the nominal injection volume is 300 μL. The various transferlines, columns and differential refractometer (the DRI detector) arecontained in an oven maintained at 135° C. Solvent for the SECexperiment is prepared by dissolving 6 grams of butylated hydroxytoluene as an antioxidant in 4 liters of Aldrich reagent grade 1,2,4trichlorobenzene (TCB). The TCB mixture is then filtered through a 0.7μm glass pre-filter and subsequently through a 0.1 μm Teflon filter. TheTCB is then degassed with an online degasser before entering the SEC.Polymer solutions are prepared by placing dry polymer in a glasscontainer, adding the desired amount of TCB, then heating the mixture at160° C. with continuous agitation for about 2 hours. All quantities aremeasured gravimetrically. The TCB densities used to express the polymerconcentration in mass/volume units are 1.463 g/mL at 25° C. and 1.324g/mL at 135° C. The injection concentration is from 1.0 to 2.0 mg/mL,with lower concentrations being used for higher molecular weightsamples. Prior to running each sample the DRI detector and the injectorare purged. Flow rate in the apparatus is then increased to 0.5mL/minute, and the DRI is allowed to stabilize for 8 to 9 hours beforeinjecting the first sample. The concentration, c, at each point in thechromatogram is calculated from the baseline-subtracted DRI signal,I_(DRI), using the following equation:

c=K _(DRI) I _(DRI)/(dn/dc)

where K_(DRI) is a constant determined by calibrating the DRI, and(dn/dc) is the refractive index increment for the system. The refractiveindex, n=1.500 for TCB at 135° C. and λ=690 nm. For purposes of thisinvention and the claims thereto, (dn/dc)=0.104 for propylene polymersand ethylene polymers, and 0.1 otherwise. Units of parameters usedthroughout this description of the SEC method are: concentration isexpressed in g/cm³, molecular weight is expressed in g/mol, andintrinsic viscosity is expressed in dL/g.

The branching index (g′(vis)) is calculated using the output of theSEC-DRI-LS-VIS method as follows. The average intrinsic viscosity,[η]avg, of the sample is calculated by:

$\lbrack\eta\rbrack_{avg} = \frac{\sum{c_{i}\lbrack\eta\rbrack}_{i}}{\sum c_{i}}$

where the summations are over the chromatographic slices, i, between theintegration limits.

The branching index g′(vis) is defined as:

${g^{\prime}{vis}} = \frac{\lbrack\eta\rbrack_{avg}}{k\; M_{v}^{\alpha}}$

where, for purpose of this invention and claims thereto, α=0.695 andk=0.000579 for linear ethylene polymers, α=0.705 and k=0.000262 forlinear propylene polymers, and α=0.695 and k=0.000181 for linear butenepolymers. My is the viscosity-average molecular weight based onmolecular weights determined by LS analysis. See Macromolecules, 2001,34, pp. 6812-6820 and Macromolecules, 2005, 38, pp. 7181-7183, forguidance on selecting a linear standard having similar molecular weightand comonomer content, and determining k coefficients and α exponents.

In an embodiment, the polyolefin is derived from a vinyl terminatedpropylene polymer. In an embodiment, the vinyl terminated propylenepolymer is produced using a process comprising: contacting propylene,under polymerization conditions, with a catalyst system comprising anactivator and at least one metallocene compound represented by theformula:

where:M is hafnium or zirconium;each X is, independently, selected from the group consisting ofhydrocarbyl radicals having from 1 to 20 carbon atoms, hydrides, amides,alkoxides, sulfides, phosphides, halides, dienes, amines, phosphines,ethers, and a combination thereof, (two X's may form a part of a fusedring or a ring system);each R¹ is, independently, a C₁ to C₁₀ alkyl group;each R² is, independently, a C₁ to C₁₀ alkyl group;each R³ is hydrogen;each R⁴, R⁵, and R⁶, is, independently, hydrogen or a substitutedhydrocarbyl or unsubstituted hydrocarbyl group, or a heteroatom;T is a bridging group;further provided that any of adjacent R⁴, R⁵, and R⁶ groups may form afused ring or multicenter fused ring system where the rings may bearomatic, partially saturated or saturated; andobtaining a propylene polymer having at least 50% allyl chain ends(relative to total unsaturations), as described in U.S. Pat. No.8,455,597, which is incorporated by reference in its entirety herein.

In an embodiment, the vinyl terminated propylene polymer is producedusing a process comprising:

1) contacting:

a) one or more olefins with

b) a transition metal catalyst compound represented by the formula:

whereinM is hafnium or zirconium;each X is, independently, selected from the group consisting ofhydrocarbyl radicals having from 1 to 20 carbon atoms, hydrides, amides,alkoxides, sulfides, phosphides, halogens, dienes, amines, phosphines,ethers, or a combination thereof;each R¹ and R³ are, independently, a C₁ to C₈ alkyl group; andeach R², R⁴, R⁵, R⁶, R⁷, R⁸, R⁹, R¹⁰, R¹¹, R¹², R¹³, and R¹⁴ are,independently, hydrogen, or a substituted or unsubstituted hydrocarbylgroup having from 1 to 8 carbon atoms, provided however that at leastthree of the R¹⁰-R¹⁴ groups are not hydrogen; and2) obtaining vinyl terminated polymer having an Mn of 300 g/mol or moreand at least 30% allyl chain ends (relative to total unsaturation), asdescribed in U.S. Pat. No. 8,318,998, which is incorporated by referencein its entirety herein.

In an embodiment, the polyolefin chain is derived from a higher olefincopolymer comprising allyl chain ends. In an embodiment, the higherolefin copolymer comprising allyl chain ends has an Mn of 300 g/mol ormore (measured by ¹H NMR) comprising:

(i) from about 20 to about 99.9 mol % of at least one C₅ to C₄₀ higherolefin; and(ii) from about 0.1 mol % to about 80 mol % of propylene;wherein the higher olefin copolymer has at least 40% allyl chain ends,as described in U.S. Pat. No. 8,399,724, which is incorporated byreference in its entirety herein.

In an embodiment, the polyolefin chain is derived from a vinylterminated branched polyolefin. In an embodiment, the vinyl terminatedbranched polyolefin has an Mn (¹H NMR) of 7,500 to 60,000 g/mol,comprising one or more alpha olefin derived units comprising ethyleneand/or propylene, and having;

(i) 50% or greater allyl chain ends, relative to total number ofunsaturated chain ends; and(ii) a g′_(vis) of 0.90 or less, as described in U.S. Publication No.2012-0245299, which is incorporated by reference in its entirety herein.

In an embodiment, the polyolefin chain is derived from a vinylterminated branched polyolefin produced by a process for polymerization,comprising:

(i) contacting, at a temperature greater than 35° C., one or moremonomers comprising ethylene and/or propylene, with a catalyst systemcomprising a metallocene catalyst compound and an activator, wherein themetallocene catalyst compound is represented by the following formula:

where:M is selected from the group consisting of zirconium or hafnium;each X is, independently, selected from the group consisting ofhydrocarbyl radicals having from 1 to 20 carbon atoms, hydrides, amides,alkoxides, sulfides, phosphides, halides, dienes, amines, phosphines,ethers, and a combination thereof, (two X's may form a part of a fusedring or a ring system);each R¹, R², R³, R⁴, R⁵, and R⁶, is, independently, hydrogen or asubstituted or unsubstituted hydrocarbyl group, a heteroatom orheteroatom containing group;further provided that any two adjacent R groups may form a fused ring ormulticenter fused ring system where the rings may be aromatic, partiallysaturated or saturated;further provided that any of adjacent R⁴, R⁵, and R⁶ groups may form afused ring or multicenter fused ring system where the rings may bearomatic, partially saturated or saturated;T is a bridging group represented by the formula (Ra)₂J, where J is oneor more of C, Si, Ge, N or P, and each Ra is, independently, hydrogen,halogen, C₁ to C₂₀ hydrocarbyl or a C₁ to C₂₀ substituted hydrocarbyl,provided that at least one R³ is a substituted or unsubstituted phenylgroup, if any of R¹, R², R⁴, R⁵, or R⁶ are not hydrogen;(ii) converting at least 50 mol % of the monomer to polyolefin; and(iii) obtaining a branched polyolefin having greater than 50% allylchain ends, relative to total unsaturated chain ends and a Tm of 60° C.or more, as described in U.S. Publication No. 2012-0245299, which isincorporated by reference in its entirety herein.

In an embodiment of the invention, the polyolefin is derived from avinyl terminated ethylene polymer, preferably a vinyl terminatedpolyethylene (preferably in particulate form) having:

(a) at least 60% allyl chain ends (preferably at least 65%, preferablyat least 70%, preferably at least 75%, preferably at least 80%,preferably at least 85%, preferably at least 90%, preferably at least95%, preferably at least 96%, preferably at least 97%, preferably atleast 98%, preferably at least 99%, or preferably at least 100%);

(b) a molecular weight distribution of less than or equal to 4.0(preferably less than or equal to 3.8, preferably less than or equal to3.5, preferably less than or equal to 3.2, preferably less than or equalto 3.0, preferably less than or equal to 2.8, or preferably less than orequal to 2.5);

(c) an Mn (¹H NMR) of at least 20,000 g/mol (preferably at least 25,000g/mol, preferably at least 30,000 g/mol, preferably at least 40,000g/mol, preferably at least 50,000 g/mol, and, optionally, less than125,000 g/mol, preferably less than 120,000, or preferably less than110,000);

(d) optionally, an Mn (GPC)/Mn (¹H NMR) in the range of from about 0.8to about 1.2 (preferably from about from 0.9 to about 1.1, preferablyfrom about 0.95 to about 1.1); and

(e) optionally, a g′(vis) of greater than 0.95 (preferably greater than0.96, preferably greater than 0.98, preferably greater than 0.98, and,optionally, preferably less than or equal to 1.0).

Preferably the vinyl terminated ethylene polymers are prepared by aprocess comprising:

(a) contacting ethylene with a supported metallocene catalyst system;wherein the supported catalyst system comprises: (i) a support material;(ii) an activator having from about 1 wt % to about 14 wt %trimethylaluminum, based on the weight of the activator; (iii) ametallocene compound represented by the formula:

wherein: T is Si or Ge; each R^(A) is a C₁ to C₂₀ substituted orunsubstituted hydrocarbyl group; each R^(B) is, independently, H, or aC₁ to C₈ substituted or unsubstituted hydrocarbyl group, or a grouprepresented by the formula —CH₂R^(x); wherein R^(x) is a C₁ to C₂₀substituted or unsubstituted hydrocarbyl group, provided that at leastone RB is methyl or a group represented by the formula —CH₂R^(x); eachR^(C) is, independently, H or a C₁ to C₂₀ substituted or unsubstitutedhydrocarbyl group; each A is independently selected from the groupconsisting of C₁ to C₂₀ substituted or unsubstituted hydrocarbyl groups,hydrides, amides, amines, alkoxides, sulfides, phosphides, halides,dienes, phosphines, and ethers; each X is, independently, hydrogen,halogen or a C₁ to C₂₀ hydrocarbyl, and two X groups can form a cyclicstructure including aromatic, partially saturated, or saturated cyclicor fused ring system; further provided that any of adjacent RA, RB,and/or RC groups may form a fused ring or multicenter fused ringsystems, where the rings may be substituted or unsubstituted, and may bearomatic, partially unsaturated, or unsaturated; and

(b) obtaining a vinyl terminated polyethylene having: (i) at least 60%allyl chain ends; (ii) a molecular weight distribution of less than orequal to 4.0; and (iii) a Mn (¹H NMR) of at least 20,000 g/mol.Preferably the vinyl terminated ethylene polymers are made according theprocess (and using the catalyst systems) described in (U.S. Ser. No.61/704,606, filed Sep. 24, 2012, entitled Production of Vinyl TerminatedPolyethylene Using Supported Catalyst System and having Attorney DocketNumber 2012EM184).

In an embodiment of the invention, the polyolefin is derived from avinyl terminated ethylene polymer, preferably a vinyl terminatedpolyethylene having: (i) at least 50% allyl chain ends (preferably 60%,70%, 80%, 90%, 95%, 96%, 97%, 98%, 99%, or 100%); (ii) a molecularweight distribution of less than or equal to 4.0 (preferably less thanor equal to 3.8, 3.6, 3.5, 3.4, 3.2, 3.0, 2.8, or 2.5); (iii) a g′(vis)of 0.95 or less (preferably less than 0.93, 0.90, 0.88, or 0.85); (iv)an Mn (¹H NMR) of at least 7,000 g/mol (preferably at least 10,000g/mol, 15,000 g/mol, 20,000 g/mol, 25,000 g/mol, 30,000 g/mol, 45,000g/mol, 55,000 g/mol, 65,000 g/mol, or 85,000 g/mol, and, optionally,less than 125,000 g/mol); and (v) a Mn (GPC)/Mn (¹H NMR) in the range offrom about 0.8 to about 1.2 (preferably from 0.85 to 1.15, 0.90 to 1.10,and 0.95 to 1.00). Preferably the vinyl terminated ethylene polymers areproduced by a process comprising:

(a) contacting ethylene with a metallocene catalyst system;wherein the catalyst system comprises:

(i) an ionizing activator;

(ii) a metallocene compound represented by the formula:

wherein T is Si or Ge; each R^(A) is a C₁ to C₂₀ substituted orunsubstituted hydrocarbyl group; each R^(B) is, independently, H or a C₁to C₈ substituted or unsubstituted hydrocarbyl group, or a grouprepresented by the formula —CH₂Rx; wherein R^(x) is a C₁ to C₂₀substituted or unsubstituted hydrocarbyl group, provided that at leastone R^(B) is methyl or a group represented by the formula —CH₂R^(x);each R^(C) is, independently, H or a C₁ to C₂₀ substituted orunsubstituted hydrocarbyl group; each A is independently selected fromthe group consisting of C₁ to C₂₀ substituted or unsubstitutedhydrocarbyl groups, hydrides, amides, amines, alkoxides, sulfides,phosphides, halides, dienes, phosphines, and ethers; each X is,independently, hydrogen, halogen, or a C₁ to C₂₀ hydrocarbyl, and two Xgroups can form a cyclic structure including aromatic, partiallysaturated, or saturated cyclic or fused ring system; further providedthat any of adjacent R^(A), R^(B), and/or R^(C) groups may form a fusedring or multicenter fused ring systems, where the rings may besubstituted or unsubstituted, and may be aromatic, partiallyunsaturated, or unsaturated; and(b) obtaining a vinyl terminated polyethylene having: (i) at least 50%allyl chain ends; (ii) a molecular weight distribution of less than orequal to 4.0; (iii) a g′(vis) of 0.95 or less; and (iv) a Mn (¹H NMR) ofat least 7,000 g/mol; and (e) a Mn (GPC)/Mn (¹H NMR) in the range offrom about 0.8 to about 1.2. Preferably the vinyl terminated ethylenepolymers are made according the process (and using the catalyst systems)described in (U.S. Ser. No. 61/704,604, filed Sep. 24, 2012, entitledProduction of Vinyl Terminated Polyethylene and having Attorney DocketNumber 2012EM185).

In any of the polymerizations described herein, the activator may be analumoxane, an aluminum alkyl, a stoichiometric activator (also referredto as an ionizing activator), which may be neutral or ionic, and/or aconventional-type cocatalyst, unless otherwise stated. Preferredactivators typically include alumoxane compounds, modified alumoxanecompounds, stoichiometric activators, and ionizing anion precursorcompounds that abstract one reactive, σ-bound, metal ligand making themetal complex cationic and providing a charge-balancing noncoordinatingor weakly coordinating anion.

Alumoxane Activators

In an embodiment of the invention, alumoxane activators are utilized asan activator in the catalyst composition, preferably methylalumoxane(MAO), modified methylalumoxane (MMAO), ethylalumoxane, and/orisobutylalumoxane. Preferably, the activator is a TMA-depleted activator(where TMA means trimethylaluminum). Any method known in the art toremove TMA may be used. For example, to produce a TMA-depletedactivator, a solution of alumoxane (such as methylalumoxane), forexample, 30 wt % in toluene may be diluted in toluene and the aluminumalkyl (such as TMA in the case of MAO) is removed from the solution, forexample, by combination with trimethylphenol and filtration of thesolid. In such embodiments, the TMA-depleted activator comprises fromabout 1 wt % to about 14 wt % trimethylaluminum (preferably less than 13wt %, preferably less than 12 wt %, preferably less than 10 wt %,preferably less than 5 wt %, or preferably 0 wt %, or, optionally,greater than 0 wt % or greater than 1 wt %).

Stoichiometric Activators

The catalyst systems useful herein may comprise one or morestoichiometric activators. A stoichiometric activator is a non-alumoxanecompound which when combined in a reaction with the catalyst compound(such as a metallocene compound) forms a catalytically active species,typically at molar ratios of stoichiometric activator to metallocenecompound of 10:1 or less (preferably 5:1, more preferably 2:1, or evenmore preferably 1:1), however is within the scope of this invention touse a molar ratio of stoichiometric activator to metallocene compound ofgreater than 10:1 as well. Useful stoichiometric (or non-alumoxane)activator-to-catalyst ratios range from 0.5:1 to 10:1, preferably 1:1 to5:1, although ranges of from 0.1:1 to 100:1, alternately from 0.5:1 to200:1, alternately from 1:1 to 500:1 alternately from 1:1 to 1000:1 maybe used.

Stoichiometric activators are non-alumoxane compounds which may beneutral or ionic, such as tri(n-butyl)ammoniumtetrakis(pentafluorophenyl)borate, a tris perfluorophenyl boronmetalloid precursor, or a tris perfluoronaphthyl boron metalloidprecursor, polyhalogenated heteroborane anions (WO 98/43983), boric acid(U.S. Pat. No. 5,942,459), or a combination thereof. It is also withinthe scope of this invention to use stoichiometric activators alone or incombination with alumoxane or modified alumoxane activators.

Neutral Stoichiometric Activators

Examples of neutral stoichiometric activators include tri-substitutedboron, tellurium, aluminum, gallium and indium or mixtures thereof. Thethree substituent groups are each independently selected from alkyls,alkenyls, halogens, substituted alkyls, aryls, arylhalides, alkoxy, andhalides. Preferably, the three groups are independently selected fromhalogen, mono or multicyclic (including halosubstituted) aryls, alkyls,and alkenyl compounds, and mixtures thereof, preferred are alkenylgroups having 1 to 20 carbon atoms, alkyl groups having 1 to 20 carbonatoms, alkoxy groups having 1 to 20 carbon atoms, and aryl groups having3 to 20 carbon atoms (including substituted aryls). More preferably, thethree groups are alkyls having 1 to 4 carbon groups, phenyl, naphthyl,or mixtures thereof. Even more preferably, the three groups arehalogenated, preferably fluorinated, aryl groups. Most preferably, theneutral stoichiometric activator is tris perfluorophenyl boron or trisperfluoronaphthyl boron.

Ionic Stoichiometric Activators

Ionic stoichiometric activators may contain an active proton, or someother cation associated with, but not coordinated to, or only looselycoordinated to, the remaining anion of the activator. Such compounds andthe like are described in European publications EP 0 570 982 A; EP 0 520732 A; EP 0 495 375 A; EP 0 500 944 B1; EP 0 277 003 A; EP 0 277 004 A;U.S. Pat. Nos. 5,153,157; 5,198,401; 5,066,741; 5,206,197; 5,241,025;5,384,299; 5,502,124; and U.S. patent application Ser. No. 08/285,380,filed Aug. 3, 1994; all of which are herein fully incorporated byreference.

Ionic stoichiometric activators comprise a cation, which is preferably aBronsted acid capable of donating a proton, and a compatiblenon-coordinating anion. Preferably, the anion is relatively large(bulky), capable of stabilizing the catalytically active species(preferably a group 4 catalytically active species) which is formed whenthe catalyst (such as a metallocene compound) and the stoichiometricactivator are combined. Preferably the anion will be sufficiently labileto be displaced by olefinic, diolefinic and acetylenically unsaturatedsubstrates or other neutral Lewis bases, such as ethers, amines, and thelike. Two classes of useful compatible non-coordinating anions have beendisclosed in EP 0 277,003 A and EP 0 277,004 A: 1) anionic coordinationcomplexes comprising a plurality of lipophilic radicals covalentlycoordinated to and shielding a central charge-bearing metal or metalloidcore, and 2) anions comprising a plurality of boron atoms, such ascarboranes, metallacarboranes, and boranes.

Ionic stoichiometric activators comprise an anion, preferably anon-coordinating anion. The term “non-coordinating anion” (NCA) means ananion which either does not coordinate to said cation or which is onlyweakly coordinated to said cation thereby remaining sufficiently labileto be displaced by a neutral Lewis base. “Compatible” non-coordinatinganions are those which are not degraded to neutrality when the initiallyformed complex decomposes. Further, the anion will not transfer ananionic substituent or fragment to the cation so as to cause it to forma neutral four coordinate metallocene compound and a neutral by-productfrom the anion. Non-coordinating anions useful in accordance with thisinvention are those that are compatible, stabilize the catalyst (such asmetallocene) cation in the sense of balancing its ionic charge at +1,yet retain sufficient lability to permit displacement by anethylenically or acetylenically unsaturated monomer duringpolymerization.

In a preferred embodiment of this invention, the ionic stoichiometricactivators are represented by the following formula (I):

(Z)_(d) ⁺ A ^(d−),  (1)

wherein (Z)_(d) ⁺ is the cation component and A^(d−) is the anioncomponent; where Z is (L—H) or a reducible Lewis Acid, L is an neutralLewis base; H is hydrogen; (L—H)⁺ is a Bronsted acid; A^(d−) is anon-coordinating anion having the charge d−; and d is an integer from 1to 3.

When Z is (L—H) such that the cation component is (L—H)_(d) ⁺, thecation component may include Bronsted acids such as protonated Lewisbases capable of protonating a moiety, such as an alkyl or aryl, fromthe bulky ligand metallocene containing transition metal catalystprecursor, resulting in a cationic transition metal species. Preferably,the activating cation (L—H)_(d) ⁺ is a Bronsted acid, capable ofdonating a proton to the transition metal catalytic precursor resultingin a transition metal cation, including ammoniums, oxoniums,phosphoniums, silyliums, and mixtures thereof, preferably ammoniums ofmethylamine, aniline, dimethylamine, diethylamine, N-methylaniline,diphenylamine, trimethylamine, triethylamine, N,N-dimethylaniline,methyldiphenylamine, pyridine, p-bromo N,N-dimethylaniline,p-nitro-N,N-dimethylaniline, phosphoniums from triethylphosphine,triphenylphosphine, and diphenylphosphine, oxoniums from ethers, such asdimethyl ether diethyl ether, tetrahydrofuran, and dioxane, sulfoniumsfrom thioethers, such as diethyl thioethers and tetrahydrothiophene, andmixtures thereof.

When Z is a reducible Lewis acid, (Z)_(d) ⁺ is preferably represented bythe formula: (Ar₃C)⁺, where Ar is aryl or aryl substituted with aheteroatom, a C₁ to C₄₀ hydrocarbyl, or a substituted C₁ to C₄₀hydrocarbyl, preferably (Z)_(d) ⁺ is represented by the formula:(Ph₃C)⁺, where Ph is phenyl or phenyl substituted with a heteroatom, aC₁ to C₄₀ hydrocarbyl, or a substituted C₁ to C₄₀ hydrocarbyl. In apreferred embodiment, the reducible Lewis acid is triphenyl carbenium.

The anion component A^(d−) includes those having the formula[M^(k+)Q_(n)]^(d−) wherein k is 1, 2, or 3; n is 1, 2, 3, 4, 5, or 6,preferably 3, 4, 5 or 6; (n−k)=d; M is an element selected from group 13of the Periodic Table of the Elements, preferably boron or aluminum; andeach Q is, independently, a hydride, bridged or unbridged dialkylamido,halide, alkoxide, aryloxide, hydrocarbyl, substituted hydrocarbyl,halocarbyl, substituted halocarbyl, and halosubstituted-hydrocarbylradicals, said Q having up to 20 carbon atoms with the proviso that innot more than one occurrence is Q a halide, and two Q groups may form aring structure. Preferably, each Q is a fluorinated hydrocarbyl grouphaving 1 to 20 carbon atoms, more preferably each Q is a fluorinatedaryl group, and most preferably each Q is a pentafluoryl aryl group.Examples of suitable A^(d−) components also include diboron compounds asdisclosed in U.S. Pat. No. 5,447,895, which is fully incorporated hereinby reference.

In other embodiments of this invention, the ionic stoichiometricactivator may be an activator comprising expanded anions, represented bythe formula:

(A*+a)_(b)(Z*J* _(j))^(−c) _(d),

wherein A* is a cation having charge +a; Z* is an anion group of from 1to 50 atoms not counting hydrogen atoms, further containing two or moreLewis base sites; J* independently each occurrence is a Lewis acidcoordinated to at least one Lewis base site of Z*, and optionally two ormore such J* groups may be joined together in a moiety having multipleLewis acid functionality; j is a number from 2 to 12; and a, b, c, and dare integers from 1 to 3, with the proviso that axb is equal to cxd.Examples of such activators comprising expandable anions may be found inU.S. Pat. No. 6,395,671, which is fully incorporated herein byreference.

Examples of ionic stoichiometric activators useful in the catalystsystem of this invention are: trimethylammonium tetraphenylborate,triethylammonium tetraphenylborate, tripropylammonium tetraphenylborate,tri(n-butyl)ammonium tetraphenylborate, tri(t-butyl)ammoniumtetraphenylborate, N,N-dimethylanilinium tetraphenylborate,N,N-diethylanilinium tetraphenylborate,N,N-dimethyl-(2,4,6-trimethylanilinium) tetraphenylborate, tropilliumtetraphenylborate, triphenylcarbenium tetraphenylborate,triphenylphosphonium tetraphenylborate triethylsilyliumtetraphenylborate, benzene(diazonium)tetraphenylborate,trimethylammonium tetrakis(pentafluorophenyl)borate, triethylammoniumtetrakis(pentafluorophenyl)borate, tripropylammoniumtetrakis(pentafluorophenyl)borate, tri(n-butyl)ammoniumtetrakis(pentafluorophenyl)borate, tri(sec-butyl)ammoniumtetrakis(pentafluorophenyl)borate, N,N-dimethylaniliniumtetrakis(pentafluorophenyl)borate, N,N-diethylaniliniumtetrakis(pentafluorophenyl)borate,N,N-dimethyl-(2,4,6-trimethylanilinium)tetrakis(pentafluorophenyl)borate,tropillium tetrakis(pentafluorophenyl)borate, triphenylcarbeniumtetrakis(pentafluorophenyl)borate, triphenylphosphoniumtetrakis(pentafluorophenyl)borate, triethylsilyliumtetrakis(pentafluorophenyl)borate,benzene(diazonium)tetrakis(pentafluorophenyl)borate, trimethylammoniumtetrakis-(2,3,4,6-tetrafluorophenyl)borate, triethylammoniumtetrakis-(2,3,4,6-tetrafluorophenyl)borate, tripropylammoniumtetrakis-(2,3,4,6-tetrafluorophenyl)borate, tri(n-butyl)ammoniumtetrakis-(2,3,4,6-tetrafluoro-phenyl)borate, dimethyl(t-butyl)ammoniumtetrakis-(2,3,4,6-tetrafluorophenyl)borate, N,N-dimethylaniliniumtetrakis-(2,3,4,6-tetrafluorophenyl)borate, N,N-diethylaniliniumtetrakis-(2,3,4,6-tetrafluorophenyl)borate,N,N-dimethyl-(2,4,6-trimethylanilinium)tetrakis-(2,3,4,6-tetrafluorophenyl)borate,tropillium tetrakis-(2,3,4,6-tetrafluorophenyl)borate,triphenylcarbenium tetrakis-(2,3,4,6-tetrafluorophenyl)borate,triphenylphosphonium tetrakis-(2,3,4,6-tetrafluorophenyl)borate,triethylsilylium tetrakis-(2,3,4,6-tetrafluorophenyl)borate,benzene(diazonium)tetrakis-(2,3,4,6-tetrafluorophenyl)borate,trimethylammonium tetrakis(perfluoronaphthyl)borate, triethylammoniumtetrakis(perfluoronaphthyl)borate, tripropylammoniumtetrakis(perfluoronaphthyl)borate, tri(n-butyl)ammoniumtetrakis(perfluoronaphthyl)borate, tri(t-butyl)ammoniumtetrakis(perfluoronaphthyl)borate, N,N-dimethylaniliniumtetrakis(perfluoronaphthyl)borate, N,N-diethylaniliniumtetrakis(perfluoronaphthyl)borate,N,N-dimethyl-(2,4,6-trimethylanilinium)tetrakis(perfluoronaphthyl)borate,tropillium tetrakis(perfluoronaphthyl)borate, triphenylcarbeniumtetrakis(perfluoronaphthyl)borate, triphenylphosphoniumtetrakis(perfluoronaphthyl)borate, triethylsilyliumtetrakis(perfluoronaphthyl)borate, benzene(diazonium)tetrakis(perfluoronaphthyl)borate, trimethylammoniumtetrakis(perfluorobiphenyl)borate, triethylammoniumtetrakis(perfluorobiphenyl)borate, tripropylammoniumtetrakis(perfluorobiphenyl)borate, tri(n-butyl)ammoniumtetrakis(perfluorobiphenyl)borate, tri(t-butyl)ammoniumtetrakis(perfluorobiphenyl)borate, N,N-dimethylaniliniumtetrakis(perfluorobiphenyl)borate, N,N-diethylaniliniumtetrakis(perfluorobiphenyl)borate,N,N-dimethyl-(2,4,6-trimethylanilinium)tetrakis(perfluorobiphenyl)borate,tropillium tetrakis(perfluorobiphenyl)borate, triphenylcarbeniumtetrakis(perfluorobiphenyl)borate, triphenylphosphoniumtetrakis(perfluorobiphenyl)borate, triethylsilyliumtetrakis(perfluorobiphenyl)borate,benzene(diazonium)tetrakis(perfluorobiphenyl)borate, trimethylammoniumtetrakis(3,5-bis(trifluoromethyl)phenyl)borate, triethylammoniumtetrakis(3,5-bis(trifluoromethyl)phenyl)borate, tripropylammoniumtetrakis(3,5-bis(trifluoromethyl)phenyl)borate, tri(n-butyl)ammoniumtetrakis(3,5-bis(trifluoromethyl)phenyl)borate, tri(t-butyl)ammoniumtetrakis(3,5-bis(trifluoromethyl)phenyl)borate, N,N-dimethylaniliniumtetrakis(3,5-bis(trifluoromethyl)phenyl)borate, N,N-diethylaniliniumtetrakis(3,5-bis(trifluoromethyl)phenyl)borate,N,N-dimethyl-(2,4,6-trimethylanilinium)tetrakis(3,5-bis(trifluoromethyl)phenyl)borate,tropillium tetrakis(3,5-bis(trifluoromethyl)phenyl)borate,triphenylcarbenium tetrakis(3,5-bis(trifluoromethyl)phenyl)borate,triphenylphosphonium tetrakis(3,5-bis(trifluoromethyl)phenyl)borate,triethylsilylium tetrakis(3,5-bis(trifluoromethyl)phenyl)borate,benzene(diazonium)tetrakis(3,5-bis(trifluoromethyl)phenyl)borate, anddialkyl ammonium salts such as: di-(i-propyl)ammoniumtetrakis(pentafluorophenyl)borate, and dicyclohexylammoniumtetrakis(pentafluorophenyl)borate; and additional tri-substitutedphosphonium salts such as tri(o-tolyl)phosphoniumtetrakis(pentafluorophenyl)borate, andtri(2,6-dimethylphenyl)phosphonium tetrakis(pentafluorophenyl)borate.

Most preferably, the ionic stoichiometric activator isN,N-dimethylanilinium tetrakis(perfluoronaphthyl)borate,N,N-dimethylanilinium tetrakis(perfluorobiphenyl)borate,N,N-dimethylanilinium tetrakis(3,5-bis(trifluoromethyl)phenyl)borate,triphenylcarbenium tetrakis(perfluoronaphthyl)borate, triphenylcarbeniumtetrakis(perfluorobiphenyl)borate, triphenylcarbeniumtetrakis(3,5-bis(trifluoromethyl)phenyl)borate, or triphenylcarbeniumtetrakis(perfluorophenyl)borate.

Bulky Ionic Stoichiometric Activators

“Bulky activator” as used herein refers to ionic stoichiometricactivators represented by the formula:

where:each R₁ is, independently, a halide, preferably a fluoride;each R₂ is, independently, a halide, a C₆ to C₂₀ substituted aromatichydrocarbyl group or a siloxy group of the formula —O—Si—R_(a), whereR_(a) is a C₁ to C₂₀ substituted or unsubstituted hydrocarbyl orhydrocarbylsilyl group (preferably R₂ is a fluoride or a perfluorinatedphenyl group);each R₃ is a halide, C₆ to C₂₀ substituted aromatic hydrocarbyl group ora siloxy group of the formula —O—Si—R_(a), where R_(a) is a C₁ to C₂₀substituted or unsubstituted hydrocarbyl or hydrocarbylsilyl group(preferably R₃ is a fluoride or a C₆ perfluorinated aromatic hydrocarbylgroup); wherein R₂ and R₃ can form one or more saturated or unsaturated,substituted or unsubstituted rings (preferably R₂ and R₃ form aperfluorinated phenyl ring);(Z)_(d) ⁺ is the cation component; where Z is (L—H) or a reducible LewisAcid, L is an neutral Lewis base; H is hydrogen; (L—H)⁺ is a Bronstedacid; and d is an integer from 1 to 3; wherein the boron anion componenthas a molecular weight of greater than 1020 g/mol; and wherein at leastthree of the substituents on the B atom each have a molecular volume ofgreater than 250 cubic Å, alternately greater than 300 cubic Å, oralternately greater than 500 cubic Å.

“Molecular volume” is used herein as an approximation of spatial stericbulk of an activator molecule in solution. Comparison of substituentswith differing molecular volumes allows the substituent with the smallermolecular volume to be considered “less bulky” in comparison to thesubstituent with the larger molecular volume. Conversely, a substituentwith a larger molecular volume may be considered “more bulky” than asubstituent with a smaller molecular volume.

Molecular volume may be calculated as reported in “A Simple ‘Back of theEnvelope’ Method for Estimating the Densities and Molecular Volumes ofLiquids and Solids,” Journal of Chemical Education, Vol. 71, No. 11,November 1994, pp. 962-964. Molecular volume (MV), in units of cubic A,is calculated using the formula: MV=8.3V_(S), where V_(S) is the scaledvolume. V_(S) is the sum of the relative volumes of the constituentatoms, and is calculated from the molecular formula of the substituentusing the following table of relative volumes. For fused rings, theV_(S) is decreased by 7.5% per fused ring.

Element Relative Volume H 1 1st short period, Li to F 2 2nd shortperiod, Na to Cl 4 1st long period, K to Br 5 2nd long period, Rb to I7.5 3rd long period, Cs to Bi 9

Exemplary bulky substituents of activators suitable herein and theirrespective scaled volumes and molecular volumes are shown in the tablebelow. The dashed bonds indicate binding to boron, as in the generalformula above.

Molecular MV Formula Per Total Structure of boron of each subst. MVActivator substituents substituent V_(s) (Å³) (Å³) Dimethylaniliniumtetrakis(perfluoronaphthyl)borate

C₁₀F₇ 34 261 1044 Dimethylanilinium tetrakis(perfluorobiphenyl)borate

C₁₂F₉ 42 349 1396 [4-tButyl-PhNMe₂H] [(C₆F₃(C₆F₅)₂)₄B]

C₁₈F₁₃ 62 515 2060

Exemplary bulky ionic stoichiometric activators useful in catalystsystems herein include: trimethylammoniumtetrakis(perfluoronaphthyl)borate, triethylammoniumtetrakis(perfluoronaphthyl)borate, tripropylammoniumtetrakis(perfluoronaphthyl)borate, tri(n-butyl)ammoniumtetrakis(perfluoronaphthyl)borate, tri(t-butyl)ammoniumtetrakis(perfluoronaphthyl)borate, N,N-dimethylaniliniumtetrakis(perfluoronaphthyl)borate, N,N-diethylaniliniumtetrakis(perfluoronaphthyl)borate,N,N-dimethyl-(2,4,6-trimethylanilinium)tetrakis(perfluoronaphthyl)borate,tropillium tetrakis(perfluoronaphthyl)borate, triphenylcarbeniumtetrakis(perfluoronaphthyl)borate, triphenylphosphoniumtetrakis(perfluoronaphthyl)borate, triethylsilyliumtetrakis(perfluoronaphthyl)borate,benzene(diazonium)tetrakis(perfluoronaphthyl)borate, trimethylammoniumtetrakis(perfluorobiphenyl)borate, triethylammoniumtetrakis(perfluorobiphenyl)borate, tripropylammoniumtetrakis(perfluorobiphenyl)borate, tri(n-butyl)ammoniumtetrakis(perfluorobiphenyl)borate, tri(t-butyl)ammoniumtetrakis(perfluorobiphenyl)borate, N,N-dimethylaniliniumtetrakis(perfluorobiphenyl)borate, N,N-diethylaniliniumtetrakis(perfluorobiphenyl)borate,N,N-dimethyl-(2,4,6-trimethylanilinium)tetrakis(perfluorobiphenyl)borate,tropillium tetrakis(perfluorobiphenyl)borate, triphenylcarbeniumtetrakis(perfluorobiphenyl)borate, triphenylphosphoniumtetrakis(perfluorobiphenyl)borate, triethylsilyliumtetrakis(perfluorobiphenyl)borate,benzene(diazonium)tetrakis(perfluorobiphenyl)borate,[4-t-butyl-PhNMe₂H][(C₆F₃(C₆F₅)₂)₄B], (where Ph is phenyl and Me ismethyl), and the types disclosed in U.S. Pat. No. 7,297,653.

In another embodiment of this invention, an activation method usingionic compounds not containing an active proton but capable of producinga bulky ligand metallocene catalyst cation and their non-coordinatinganion are also contemplated, and are described in EP 0 426 637 A, EP 0573 403 A, and U.S. Pat. No. 5,387,568, which are all hereinincorporated by reference.

In another embodiment of this invention, inventive processes also canemploy stoichiometric activator compounds that are initially neutralLewis acids but form a cationic metal complex and a noncoordinatinganion, or a zwitterionic complex upon reaction with the metallocenecompounds. For example, tris(pentafluorophenyl)boron or aluminum may actto abstract a hydrocarbyl or hydride ligand to yield an inventioncationic metal complex and stabilizing noncoordinating anion, see EP 0427 697 A and EP 0 520 732 A for illustrations of analogous group 4metallocene compounds. Also, see the methods and compounds of EP 0 495375 A. For formation of zwitterionic complexes using analogous group 4compounds, see U.S. Pat. Nos. 5,624,878; 5,486,632; and 5,527,929.

In another embodiment of this invention, another suitable ionicstoichiometric activator comprises a salt of a cationic oxidizing agentand a noncoordinating, compatible anion represented by the formula:

(X ^(e+))_(d)(A ^(d−))_(e)  (3)

wherein X^(e+) is a cationic oxidizing agent having a charge of e+; e is1, 2, or 3; A^(d−) is a non-coordinating anion having the charge d−; andd is 1, 2, or 3. Examples of X^(e+) include: ferrocenium,hydrocarbyl-substituted ferrocenium, Ag⁺, or Pb⁺². Preferred embodimentsof A^(d−) are those anions previously defined with respect to theBronsted acid containing activators, especiallytetrakis(pentafluorophenyl)borate.

Activator Combinations

It is within the scope of this invention that metallocene compounds canbe combined with one or more activators or activation methods describedabove. For example, a combination of activators have been described inU.S. Pat. Nos. 5,153,157; 5,453,410; European Publication No. EP 0 573120 B1; PCT Publication Nos. WO 94/07928; and WO 95/14044. Thesedocuments all discuss the use of an alumoxane in combination with astoichiometric activator.

In another embodiment, the vinyl terminated macromonomer may be a vinylterminated ethylene macromonomer. In some embodiments, aphenoxyimine-based catalyst (a Mitsui FI catalyst) or apyrroleimine-based catalyst (a Mitsui PI catalyst) can be used toprepare the vinyl terminated ethylene macromonomer. These catalystscomprise (a) a transition metal (preferably Ti) compound havingphenoxyimine or pyrroleimine as a ligand, and (b) one or more kind(s) ofcompound selected from (b-1) an organic metal compound, (b-2) an organicaluminumoxy compound, and (b-3) a compound that reacts with thetransition metal compound (a) to form an ion pair, as described inJP-A-2001-72706, JP-A-2002-332312, JP-A-2003-313247, JP-A-2004-107486,and JP-A-2004-107563. Herein, as the transition metal contained in thetransition metal compound, the transition metal of Groups 3 to 11 in theperiodic table can be used. Preferred catalysts to prepare the vinylterminated ethylene macromonomer include those described in U.S. Pat.No. 7,795,347, specifically at column 16, line 56 et seq. in Formula(XI).

In another embodiment, the vinyl terminated macromonomer may be a vinylterminated isotactic polypropylene or a vinyl terminated polyethylene asdisclosed in U.S. Pat. Nos. 6,444,773; 6,555,635; 6,147,180; 6,660,809;6,750,307; 6,774,191; 6,169,154; and EP 0 958 309; which areincorporated by reference herein.

In a preferred embodiment any vinyl terminated macromonomer describedherein can be fractionated or distilled by any means know in the art andone or more of the fractions may be used in the invention describedherein. Preferred fractions typically have a narrow Mw/Mn, such as lessthan 1.5, preferably 1.4 or less, preferably 1.3 or less, preferably 1.2or less. Alternately the Mw/Mn is from 1 to 1.4, preferably 1.05 to 1.3,preferably 1.1 to 1.2.

In another embodiment of the invention, the fractions have a narrowboiling point range (as determined by ASTM D86) of less than 70° C.,preferably less than 60° C., preferably less than 50° C., preferablyless than 40° C., preferably less than 30° C., preferably less than 20°C., preferably less than 10° C.

In a preferred embodiment of the invention, the vinyl terminatedmacromonomer injected into a gas chromatograph column to determine theoptimum cut points for the fractionation.

In a preferred embodiment, the fractions may be obtained by separationof the vinyl terminated macromonomer product such as by the processesdescribed in GB 1550419A, U.S. Pat. Nos. 3,647,906 and 3,592,866. Usefulfractions include ranges from about 4 carbon-numbers up to 20carbon-numbers, e.g., C₄-C₈, C₄-C₁₄, C₄-C₂₀. The lower α-olefin fractionmay contain α-olefins having the same carbon-number as the lowestα-olefin in the higher α-olefin fraction, but preferably contains onlyα-olefins of carbon-numbers lower than the carbon-number of the lowestα-olefin in the higher α-olefin fraction. The higher (α-olefin fractionmay include α-olefins of the same carbon number as the highest α-olefinin the lower α-olefin fraction up to the highest α-olefin produced inthe reaction, but generally not higher than C₄₀. Preferably, however,the higher α-olefin fraction contains only (α-olefins of carbon-numbershigher than the carbon number of the highest α-olefin in the lowerα-olefin fraction.

In a separation where an α-olefin product mixture free of lightoligomers, e.g., dimers, trimers, tetramers, etc., is desired, the lowerα-olefin fraction is further separated into a light α-olefin fractionand an intermediate α-olefin fraction. The light α-olefin fraction mayinclude from C₄ up to C₁₂, e.g., C₄-C₆, C₄-C₈, C₄-C₁₀, etc. In thismodification, the intermediate α-olefin fraction is removed as productand the light α-olefin fraction is converted to additional intermediateα-olefins.

In another embodiment, any vinyl terminated macromonomer describedherein can be separated into different boiling point cuts bydistillation performed according to the procedures described in ASTMmethods D2892 and D5236. (D2892: Standard Test Method for Distillationof Crude Petroleum (15-Theoretical Plate Column) and D5236: StandardTest Method for Distillation of Heavy Hydrocarbon Mixtures (VacuumPotstill Method).)

For example a low molecular weight atactic polypropylene VTM (677.3 gramcharge) can be fractionated or distilled using the boiling point range,mass recovery, vacuum conditions listed below. Both initial boilingpoint (IBP) and final boiling point (FBP) are in degree Fahrenheit (°F.) and corrected to atmospheric pressure.

Initial Final Weight of boiling boiling collected Still ASTM Fractionpoint/IBP point/FBP fraction pressure method (Cut) # (° F.) (° F.)(grams) (mmHg) used Charge (Feed) — — 677.3 1 IBP 140 3.8 760 D2892 2140 160 11.9 760 D2892 3 160 265 27.8 760 D2892 4 265 365 35.0 88 D28925 365 465 46.6 88 D2892 6 465 525 34.4 88 D2892 7 525 568 44.0 10 D28928 568 588 14.2 10 D2892 9 588 645 53.1 10 D2892 10  645 700 63.4 2 D289211  700 844 41.2 0.2 D5236 12  844 892 42.3 0.2 D5236 13  892 904 17.90.2 D5236 Distillation  904+ — 226.6 — — Bottoms

As shown in the table above, total recovery of collected fractions(fraction 1 to 13) with boiling points between 25° C. and 904° F. was435.6 g (64.3 wt % of initial charge). Total recovery of distillationbottoms with boiling point above 904° F. was 226.6 g (33.5 wt % ofinitial charge). The total recovery of both distilled fractions andbottoms material amounts to 97.8 wt %. The resulting distilled fractionsand distillation bottoms have narrow molecular weight distributions(Mw/Mn<1.4) as determined by GPC.

In another embodiment of the invention, the vinyl terminatedmacromonomer (preferably a propylene based vinyl terminatedmacromonomer, preferably a homopolypropylene vinyl terminatedmacromonomer) has less than 1 mol % regio defects (as determined by ¹³CNMR), based upon the total propylene monomer. Three types of defects aredefined to be the regio defects: 2,1-erythro, 2,1-threo, and3,1-isomerization. The structures and peak assignments for these aregiven in L. Resconi, L. Cavallo, A. Fait, and F. Piemontesi, Chem. Rev.2000, 100, pp. 1253-1345, as well as H. N. Cheng, Macromolecules, 17,1950 (1984). Alternately, the vinyl terminated macromonomer (preferablya propylene based vinyl terminated macromer, preferably ahomopolypropylene vinyl terminated macromonomer) has less than 250 regiodefects per 10,000 monomer units (as determined by ¹³C NMR), preferablyless than 150, preferably less than 100, preferably less than 50 regiodefects per 10,000 monomer units. The regio defects each give rise tomultiple peaks in the carbon NMR spectrum, and these are all integratedand averaged (to the extent that they are resolved from other peaks inthe spectrum), to improve the measurement accuracy. The chemical shiftoffsets of the resolvable resonances used in the analysis are tabulatedbelow. The precise peak positions may shift as a function of NMR solventchoice.

Regio defect Chemical shift range (ppm) 2,1-erythro 42.3, 38.6, 36.0,35.9, 31.5, 30.6, 17.6, 17.2 2,1-threo 43.4, 38.9, 35.6, 34.7, 32.5,31.2, 15.4, 15.0 3,1 insertion 37.6, 30.9, 27.7

The average integral for each defect is divided by the integral for oneof the main propylene signals (CH₃, CH, CH₂), and multiplied by 10000 todetermine the defect concentration per 10000 monomers.

In another embodiment, any vinyl terminated macromonomer describedherein may have a melting point (DSC first melt) of from 60° C. to 160°C., alternately 50° C. to 145° C., alternately 50° C. to 130° C.,alternately 50° C. to 100° C. In another embodiment, the vinylterminated macromonomer described herein have no detectable meltingpoint by DSC following storage at ambient temperature (23° C.) for atleast 48 hours.

In another embodiment, the vinyl terminated macromonomer describedherein may have a glass transition temperature of less than 0° C. orless (DSC), preferably −10° C. or less, more preferably −20° C. or less,more preferably −30° C. or less, more preferably −50° C. or less.

Melting temperature (T_(m)) and glass transition temperature (Tg) aremeasured using Differential Scanning calorimetry (DSC) usingcommercially available equipment such as a TA Instruments 2920 DSC.Typically, 3 to 10 mg of the sample, that has been stored at 25° C. forat least 48 hours, is sealed in an aluminum pan and loaded into theinstrument at 25° C. The sample is equilibrated at 25° C., then it iscooled at a cooling rate of 10° C./min to −80° C. The sample is held at−80° C. for 5 min and then heated at a heating rate of 10° C./min to 25°C. The glass transition temperature is measured from the heating cycle.Alternatively, the sample is equilibrated at 25° C., then heated at aheating rate of 10° C./min to 150° C. The endothermic meltingtransition, if present, is analyzed for onset of transition and peaktemperature. The melting temperatures reported are the peak meltingtemperatures from the first heat unless otherwise specified. For samplesdisplaying multiple peaks, the melting point (or melting temperature) isdefined to be the peak melting temperature (i.e., associated with thelargest endothermic calorimetric response in that range of temperatures)from the DSC melting trace.

In another embodiment, the vinyl terminated macromonomers describedherein are a liquid at 25° C.

In a particularly preferred embodiment of the invention, the vinylterminated macromonomer (preferably comprising propylene, at least 50mol % propylene, preferably at least 70 propylene) has less than 250regio defects per 10,000 monomer units, preferably less than 150,preferably less than 100, preferably less than 50 regio defects per10,000 monomer units and a Tg of less than 0° C. or less (DSC),preferably −10° C. or less, more preferably −20° C. or less, morepreferably −30° C. or less, more preferably −50° C. or less.

In another embodiment, the vinyl terminated macromonomers describedherein have a viscosity at 60° C. of greater than 1000 cP, greater than12,000 cP, or greater than 100,000 cP. In other embodiments, the vinylterminated macromonomer have a viscosity of less than 200,000 cP, lessthan 150,000 cP, or less than 100,000 cP. Viscosity is defined asresistance to flow and the melt viscosity of neat copolymers is measuredat elevated temperature using a Brookfield Digital Viscometer.

In another embodiment the VTM described herein also has a viscosity(also referred to a Brookfield Viscosity or Melt Viscosity) of 90,000mPa·sec or less at 190° C. (as measured by ASTM D 3236 at 190° C.;ASTM=American Society for Testing and Materials); or 80,000 mPa·sec orless, or 70,000 mPa·sec or less, or 60,000 mPa·sec or less, or 50,000mPa·sec or less, or 40,000 mPa·sec or less, or 30,000 mPa·sec or less,or 20,000 mPa·sec or less, or 10,000 mPa·sec or less, or 8,000 mPa·secor less, or 5,000 mPa·sec or less, or 4,000 mPa·sec or less, or 3,000mPa·sec or less, or 1,500 mPa·sec or less, or between 250 and 6,000mPa·sec, or between 500 and 5,500 mPa·sec, or between 500 and 3,000mPa·sec, or between 500 and 1,500 mPa·sec, and/or a viscosity of 8,000mPa·sec or less at 160° C. (as measured by ASTM D 3236 at 160° C.); or7,000 mPa·sec or less, or 6,000 mPa·sec or less, or 5,000 mPa·sec orless, or 4,000 mPa·sec or less, or 3,000 mPa·sec or less, or 1,500mPa·sec or less, or between 250 and 6,000 mPa·sec, or between 500 and5,500 mPa·sec, or between 500 and 3,000 mPa·sec, or between 500 and1,500 mPa·sec. In other embodiments, the viscosity is 200,000 mPa·sec orless at 190° C., depending on the application. In other embodiments, theviscosity is 50,000 mPa·sec or less depending on the applications.

Process to Functionalize Polyolefins

This invention relates to a process to functionalize polyolefinscomprising contacting a vinyl terminated macromonomer with ahydrohalogenating agent.

The reactants are typically combined in a reaction vessel at atemperature of −50° C. to 300° C. (preferably 25° C., preferably 150°C.). Likewise the reactants are typically combined at a pressure of 0 to1000 MPa (preferably 0.5 to 500 MPa, preferably 1 to 250 MPa) for aresidence time of 0.5 seconds to 10 hours (preferably 1 second to 5hours, preferably 1 minute to 1 hour).

Typically, from about 0.5 to about 1.0 moles or a slight excess of thehydrohalogenation reagent are charged to the reactor per mole of VTMcharged.

The process is typically a solution process, although it may be a bulkor high pressure process. Homogeneous processes are preferred. (Ahomogeneous process is defined to be a process where at least 90 wt % ofthe product is soluble in the reaction media.) A bulk homogeneousprocess is particularly preferred. (A bulk process is defined to be aprocess where reactant concentration in all feeds to the reactor is 70vol % or more.) Alternately, no solvent or diluent is present or addedin the reaction medium, (except for the small amounts used as thecarrier for the catalyst or other additives, or amounts typically foundwith the reactants; e.g., propane in propylene).

Suitable diluents/solvents for the process include non-coordinating,inert liquids. Examples include straight and branched-chain hydrocarbonssuch as isobutane, butane, pentane, isopentane, hexanes, isohexane,heptane, octane, dodecane, and mixtures thereof; cyclic and alicyclichydrocarbons such as cyclohexane, cycloheptane, methylcyclohexane,methylcycloheptane, and mixtures thereof such as can be foundcommercially (Isopar™); perhalogenated hydrocarbons such asperfluorinated C₄₋₁₀ alkanes, chlorobenzene, and aromatic andalkylsubstituted aromatic compounds such as benzene, toluene,mesitylene, and xylene. In a preferred embodiment, the feedconcentration for the process is 60 vol % solvent or less, preferably 40vol % or less, preferably 20 vol % or less.

The process may be batch, semi-batch or continuous. As used herein, theterm continuous means a system that operates without interruption orcessation. For example, a continuous process to produce a polymer wouldbe one where the reactants are continually introduced into one or morereactors and polymer product is continually withdrawn.

Useful reaction vessels include reactors, including continuous stirredtank reactors, batch reactors, reactive extruders, tubular reactors,pipes or pumps.

This invention further relates to a process, preferably an in-lineprocess, preferably a continuous process, to produce functionalizedpolyolefins, comprising introducing macromonomer and hydrohalogenatingagent(s) into a reactor, obtaining a reactor effluent containingfunctionalized terminated polyolefin, optionally removing (such asflashing off) solvent, unused monomer and/or other volatiles, obtainingfunctionalized terminated polyolefin (such as those described herein),preferably an in-line process, preferably a continuous process, toproduce functionalized polyolefins, comprising introducing vinylterminated polyolefin and a hydrohalogenating agent (as describedherein) into a reaction zone (such as a reactor, an extruder, a pipeand/or a pump) and obtaining functionalized polyolefin (such as thosedescribed herein).

Halides are synthesized by the hydrohalogenation of vinyl terminatedmacromonomers in high yield and purity.

Hydrohalogenation Reagents

Hydrohalogenating reagents include those known to those having ordinaryskill in the art and include HBr, HCl, HI, HF, and the like. They areoften dissolved in another acid, such as acetic acid. For example,hydrobromic acid can be prepared in water (48% HBr in water). Gaseoushydrogen bromide can be generated from metal bromide salts and strongacid such as NaBr+ concentrated H₂SO₄. Hydrogen chloride is available ashydrochloric acid, gas, in 1,4-dioxane, acetic acid, diethyl ether,methanol, ethanol, 2-propanol, or 1-butanol from Sigma Aldrich Co andother commercial suppliers.

Blends of Functionalized Polyolefins

In some embodiments, the functionalized (and optionally derivitized)polyolefins produced by this invention may be blended with from 0.5 wt %to 99 wt % (typically 1.0 wt % to 98 wt %, and ideally about 50 wt % toabout 98 wt %) of one or more other polymers, including but not limitedto, thermoplastic polymer(s) and/or elastomer(s).

By thermoplastic polymer(s) is meant a polymer that can be melted byheat and then cooled without appreciable change in properties.Thermoplastic polymers typically include, but are not limited to,polyolefins, polyamides, polyesters, polycarbonates, polysulfones,polyacetals, polylactones, acrylonitrile-butadiene-styrene resins,polyphenylene oxide, polyphenylene sulfide, styrene-acrylonitrileresins, styrene maleic anhydride, polyimides, aromatic polyketones, ormixtures of two or more of the above. Preferred polyolefins include, butare not limited to, polymers comprising one or more linear, branched orcyclic C₂ to C₄₀ olefins, preferably polymers comprising propylenecopolymerized with one or more C₃ to C₄₀ olefins, preferably a C₃ to C₂₀alpha-olefin, more preferably C₃ to C₁₀ alpha-olefins. More preferredpolyolefins include, but are not limited to, polymers comprisingethylene including but not limited to ethylene copolymerized with a C₃to C₄₀ olefin, preferably a C₃ to C₂₀ alpha-olefin, more preferablypropylene and/or butene.

By elastomers is meant all natural and synthetic rubbers, includingthose defined in ASTM D1566. Examples of preferred elastomers include,but are not limited to, ethylene propylene rubber, ethylene propylenediene monomer rubber, styrenic block copolymer rubbers (including SI,SIS, SB, SBS, SIBS, and the like, where S=styrene, I=isobutylene, andB=butadiene), butyl rubber, halobutyl rubber, copolymers of isobutyleneand para-alkylstyrene, halogenated copolymers of isobutylene andpara-alkylstyrene, natural rubber, polyisoprene, copolymers of butadienewith acrylonitrile, polychloroprene, alkyl acrylate rubber, chlorinatedisoprene rubber, acrylonitrile chlorinated isoprene rubber,polybutadiene rubber (both cis and trans).

In another embodiment, the functionalized (and optionally derivitized)polyolefins produced herein may further be combined with one or more ofpolybutene, ethylene vinyl acetate, low density polyethylene (density0.915 to less than 0.935 g/cm³) linear low density polyethylene, ultralow density polyethylene (density 0.86 to less than 0.90 g/cm³), verylow density polyethylene (density 0.90 to less than 0.915 g/cm³), mediumdensity polyethylene (density 0.935 to less than 0.945 g/cm³), highdensity polyethylene (density 0.945 to 0.98 g/cm³), ethylene vinylacetate, ethylene methyl acrylate, copolymers of acrylic acid,polymethylmethacrylate or any other polymers polymerizable by ahigh-pressure free radical process, polyvinylchloride, polybutene-1,isotactic polybutene, ABS resins, ethylene-propylene rubber (EPR),vulcanized EPR, EPDM, block copolymer, styrenic block copolymers,polyamides, polycarbonates, PET resins, crosslinked polyethylene,copolymers of ethylene and vinyl alcohol (EVOH), polymers of aromaticmonomers such as polystyrene, poly-1 esters, polyacetal, polyvinylidinefluoride, polyethylene glycols and/or polyisobutylene. Preferredpolymers include those available from ExxonMobil Chemical Company inBaytown, Tex. under the tradenames EXCEED™ and EXACT™.

Tackifiers may be blended with the functionalized (and optionallyderivitized) polyolefins produced herein and/or with blends of thefunctionalized (and optionally derivitized) polyolefins produced by thisinventions (as described above). Examples of useful tackifiers include,but are not limited to, aliphatic hydrocarbon resins, aromatic modifiedaliphatic hydrocarbon resins, hydrogenated polycyclopentadiene resins,polycyclopentadiene resins, gum rosins, gum rosin esters, wood rosins,wood rosin esters, tall oil rosins, tall oil rosin esters, polyterpenes,aromatic modified polyterpenes, terpene phenolics, aromatic modifiedhydrogenated polycyclopentadiene resins, hydrogenated aliphatic resin,hydrogenated aliphatic aromatic resins, hydrogenated terpenes andmodified terpenes, and hydrogenated rosin esters. In some embodimentsthe tackifier is hydrogenated. In some embodiments the tackifier has asoftening point (Ring and Ball, as measured by ASTM E-28) of 80° C. to140° C., preferably 100° C. to 130° C. The tackifier, if present, istypically present at about 1 wt % to about 50 wt %, based upon theweight of the blend, more preferably 10 wt % to 40 wt %, even morepreferably 20 wt % to 40 wt %.

In another embodiment, the functionalized (and optionally derivitized)polyolefins of this invention, and/or blends thereof, further comprisetypical additives known in the art such as fillers, cavitating agents,antioxidants, surfactants, adjuvants, plasticizers, block, antiblock,color masterbatches, pigments, dyes, processing aids, UV stabilizers,neutralizers, lubricants, waxes, and/or nucleating agents. The additivesmay be present in the typically effective amounts well known in the art,such as 0.001 wt % to 10 wt %. Preferred fillers, cavitating agentsand/or nucleating agents include titanium dioxide, calcium carbonate,barium sulfate, silica, silicon dioxide, carbon black, sand, glassbeads, mineral aggregates, talc, clay and the like. Preferredantioxidants include phenolic antioxidants, such as Irganox 1010,Irganox, 1076 both available from Ciba-Geigy. Preferred oils includeparaffinic or naphthenic oils such as Primol 352, or Primol 876available from ExxonMobil Chemical France, S. A. in Paris, France. Morepreferred oils include aliphatic naphthenic oils, white oils or thelike.

In a particularly preferred embodiment, the functionalized (andoptionally derivitized) polyolefins produced herein are combined withpolymers (elastomeric and/or thermoplastic) having functional groupssuch as unsaturated molecules-vinyl bonds, ketones or aldehydes underconditions such that they react. Reaction may be confirmed by an atleast 20% (preferably at least 50%, preferably at least 100%) increasein Mw as compared to the Mw of the functionalized polyolefin prior toreaction. Such reaction conditions may be increased heat (for example,above the Tm of the functionalized polyolefin), increased shear (such asfrom a reactive extruder), presence or absence of solvent. Conditionsuseful for reaction include temperatures from 150° C. to 240° C. andwhere the components can be added to a stream comprising polymer andother species via a side arm extruder, gravimetric feeder, or liquidspump. Useful polymers having functional groups that can be reacted withthe functionalized polyolefins produced herein include polyesters,polyvinyl acetates, nylons (polyamides), polybutadiene, nitrile rubber,hydroxylated nitrile rubber. In some embodiments, the functionalized(and optionally derivitized) polyolefin of this invention may be blendedwith up to 99 wt % (preferably up to 25 wt %, preferably up to 20 wt %,preferably up to 15 wt %, preferably up to 10 wt %, preferably up to 5wt %), based upon the weight of the composition, of one or moreadditional polymers. Suitable polymers include those described as PM 1)to PM 7) in U.S. Pat. No. 8,003,725.

Applications

The functionalized VTMs of this invention (and blends thereof asdescribed above) may be used in any known thermoplastic or elastomerapplication. Examples include uses in molded parts, films, tapes,sheets, tubing, hose, sheeting, wire and cable coating, adhesives, shoesoles, bumpers, gaskets, bellows, films, fibers, elastic fibers,nonwovens, spunbonds, corrosion protection coatings and sealants.Preferred uses include additives for lubricants and/or fuels.

In some embodiments the functionalized vinyl terminated macromonomersproduced herein are further functionalized (derivitized), such asdescribed in U.S. Pat. No. 6,022,929; A. Toyota, T. Tsutsui, and N.Kashiwa, Polymer Bulletin 48, pp. 213-219, 2002; J. Am. Chem. Soc.,1990, 112, pp. 7433-7434; and U.S. Pat. No. 8,399,725.

The functionalized vinyl terminated materials prepared herein may beused in oil additivation, lubricants, fuels and many other applications.Preferred uses include additives for lubricants and or fuels.

In particular embodiments herein, the vinyl terminated macromonomersdisclosed herein, or functionalized/derivitized analogs thereof, areuseful as additives, preferably in a lubricant.

The functionalized VTM's and/or derivitized VTM's produced herein haveuses as lubricating additives which can act as dispersants, viscosityindex improvers, or multifunctional viscosity index improvers.Additionally they may be used as disinfectants (functionalized amines)and or wetting agents.

Functionalized VTMs and/or derivitized VTMs having uses as dispersantstypically have Mn's g/mol) of less than 20,000, preferably less than10,000 and most preferably less than 8,000 and typically can range from500 to 10,000 (e.g., 500 to 5,000), preferably from 1,000 to 8,000(e.g., 1,000 to 5,000) and most preferably from 1,500 to 6,000 (e.g.,1,500 to 3,000).

The functionalized VTMs and/or derivitized VTMs described herein havingMn's (g/mol) of greater than 10,000 g/mol, preferably greater than10,000 to 100,000 g/mol (preferably 20,000 to 60,000 g/mol) are usefulfor viscosity index improvers for lubricating oil compositions, adhesiveadditives, antifogging and wetting agents, ink and paint adhesionpromoters, coatings, tackifiers and sealants, and the like. In addition,such VTMs may be functionalized and derivitized to make multifunctionalviscosity index improvers which also possess dispersant properties. (Formore information please see U.S. Pat. No. 6,022,929.)

The functionalized VTMs and/or derivitized VTMs described herein may becombined with other additives (such as viscosity index improvers,corrosion inhibitor, oxidation inhibitor, dispersant, lube oil flowimprover, detergents, demulsifiers, rust inhibitors, pour pointdepressant, anti-foaming agents, antiwear agents, seal swellant,friction modifiers, and the like (described for example in U.S. Pat. No.6,022,929 at columns 60, line 42-column 78, line 54 and the referencescited therein) to form compositions for many applications, including butnot limited to lube oil additive packages, lube oils, and the like.

Compositions containing these additives are typically are blended into abase oil in amounts which are effective to provide their normalattendant function. Representative effective amounts of such additivesare illustrated as follows:

(Typical) (Preferred) Compositions wt %* wt %* V.I. Improver    1-12 1-4 Corrosion Inhibitor 0.01-3 0.01-1.5 Oxidation Inhibitor 0.01-50.01-1.5 Dispersant  0.1-10 0.1-5  Lube Oil Flow Improver 0.01-20.01-1.5 Detergents and Rust inhibitors 0.01-6 0.01-3   Pour PointDepressant   0.01-1.5 0.01-1.5 Anti-Foaming Agents  0.001-0.1 0.001-0.01Antiwear Agents 0.001-5  0.001-1.5  Seal Swellant  0.1-8 0.1-4  FrictionModifiers 0.01-3 0.01-1.5 Lubricating Base Oil Balance Balance *Wt %'sare based on active ingredient content of the additive, and/or upon thetotal weight of any additive-package, or formulation which will be thesum of the A.I. weight of each additive plus the weight of total oil ordiluent.

When other additives are employed, it may be desirable, although notnecessary, to prepare additive concentrates comprising concentratedsolutions or dispersions of the subject additives of this invention (inconcentrate amounts hereinabove described), together with one or more ofsaid other additives (said concentrate when constituting an additivemixture being referred to herein as an additive-package) whereby severaladditives can be added simultaneously to the base oil to form thelubricating oil composition. Dissolution of the additive concentrateinto the lubricating oil may be facilitated by solvents and by mixingaccompanied with mild heating, but this is not essential. The subjectfunctionalized or derivitized VTMs of the present invention can be addedto small amounts of base oil or other compatible solvents along withother desirable additives to form additive-packages containing activeingredients in collective amounts of typically from about 2.5% to about90%, and preferably from about 15% to about 75%, and most preferablyfrom about 25% to about 60% by weight additives in the appropriateproportions with the remainder being base oil.

The final formulations may employ typically about 10 wt % of theadditive-package with the remainder being base oil.

In another embodiment, the vinyl terminated polyolefins described hereincan be used in any process, blend or product disclosed in WO 2009/155472or U.S. Pat. No. 6,022,929, which are incorporated by reference herein.

In a preferred embodiment, this invention relates to a fuel comprisingany VTM produced herein. In a preferred embodiment, this inventionrelates to a lubricant comprising any VTM produced herein.

EXPERIMENTAL Product Characterization

Products were characterized by ¹H NMR and ¹³C NMR as follows.

¹H NMR

Unless otherwise stated, ¹H NMR data was collected at either 25° C. or120° C. (for purposes of the claims, 120° C. shall be used) in a 5 mmprobe using a spectrometer with a ¹H frequency of at least 400 MHz. Datawas recorded using a maximum pulse width of 45° and either a 1 or 2second delay between pulses. Typical NMR solvents such as CDCl₃, CD₂Cl₂,or C₆D₆ were purchased from Cambridge Isotope Laboratories orSigmaAldrich and were used at ambient temperatures in collection of theNMR data.

¹³C NMR

Unless otherwise stated, ¹³C NMR data was collected at 120° C. using aspectrometer with a ¹³C frequency of at least 100 MHz. A 90 degreepulse, an acquisition time adjusted to give a digital resolution between0.1 and 0.12 Hz, at least a 2 second pulse acquisition delay time withcontinuous broadband proton decoupling using swept square wavemodulation without gating was employed during the entire acquisitionperiod. The spectra were acquired with time averaging to provide asignal to noise level adequate to measure the signals of interest.Samples were dissolved in tetrachloroethane-d₂ (TCE) for hightemperature measurements. Other solvents such as CDCl₃, CD₂Cl₂, or C₆D₆were used at ambient temperatures.

All molecular weights are g/mol unless otherwise noted.

Weight-average molecular weight (Mw (GPC)), molecular weightdistribution (MWD), Mw (GPC)/Mn (GPC) where Mn (GPC) is thenumber-average molecular weight are characterized using a Size ExclusionChromatograph (SEC), equipped with a differential refractive indexdetector (DRI). Tetrahydrofuran (THF) solvent is used for the SECexperiment. The THF was then degassed with an inline degasser. Samplesolutions were prepared by placing the sample in a 10 ml glass vial withsolvent resistant cap, adding the desired amount of THF, then agitationfor about 1 hr. All quantities were measured gravimetrically. Theinjection concentration is 6 mg/mL. Prior to running a sample set, theDRI detector and the injector were purged. Flow rate in the apparatuswas then increased to 1.0 mL/min, and the DRI was allowed to stabilizefor 1 hr. The instrument conditions are listed in Table 1. The samplesare analyzed using a poly iso-butylene calibration.

The molecular weight averages were defined by considering thediscontinuous nature of the distribution in which the macromoleculesexist in discrete fractions i containing N_(i) molecules of molecularweight M_(i). The weight-average molecular weight, M_(w), was defined asthe sum of the products of the molecular weight M_(i) of each fractionmultiplied by its weight fraction w_(i):

M _(w) ≡Σw _(i) M _(i)=(ΣN _(i) M _(i) ² /ΣN _(i) M _(i))

since the weight fraction w_(i) is defined as the weight of molecules ofmolecular weight M_(i) divided by the total weight of all the moleculespresent:

w _(i) =N _(i) M _(i) /ΣN _(i) M _(i).

The number-average molecular weight, M_(n), is defined as the sum of theproducts of the molecular weight M_(i) of each fraction multiplied byits mole fraction x_(i):

M _(n) ≡Σx _(i) M _(i) =N _(i) M _(i) /ΣN _(i)

since the mole fraction x_(i) is defined as N_(i) divided by the totalnumber of molecules:

x _(i) =N _(i) /ΣN _(i).

GPC Conditions

INSTRUMENT# 31 Waters Alliance 2690 HPLC COLUMN Type: 3 Mixed Bed type“D” 5μ particles Length: 300 mm ID: 7.5 mm Supplier: PolymerLaboratories SOLVENT Type: 100% tetrahydrofuran un-inhibited PROGRAM(THF) Flow Rate: 1 ml./min. DETECTOR A: Waters 486 tunable UV @ 254 nm.λ B: Waters 2410 Refractive Index TEMPERATURE Injector: Ambient ~23° C.Detector: Ambient ~23° C. Column's: Ambient ~23° C. INJECTION 100 μlVOLUME SAMPLE 0.6 w/v % (6 mg./ml.) CONCENTRATION SOLVENT THF DILUENT

Example 1

Unless specified otherwise, all reagents and solvents were used asreceived. Vinyl-terminated atactic homopolypropylene macromer A, freefrom low-boiling materials, was obtained as a colorless liquid aftervolatiles had been removed from as-received macromonomer sample byheating at 85° C. to 100° C. under vacuum for several hours. Mn's ofvinyl terminated macromonomers were determined by ¹H NMR in CDCl₃.

Vinyl Terminated Macromers used were made as previously as disclosed inU.S. Pat. No. 8,318,998 and/or U.S. Pat. No. 8,455,597, which areincorporated by reference in its entirety herein.

Vinylidene aPP was similarly synthesized using the catalyst systemcomposed of a 1 to 1 molar amount of (CpHMe₄)(CpH₄n-propyl)ZrMe₂ anddimethylanilinium tetrakisperfluoronaphthylborate.

Anhydrous solvents such as toluene were purchased from Aldrich and driedover 3 A sieves. Dimethylanilinium tetrakisperfluoronaphthylborate waspurchased from Grace-Davison. (CpHMe₄)(CpH₄n-propyl)ZrMe₂ was purchasedfrom Boulder.

Starting Materials

-   -   aPP-VTM (Macromer A), M_(n)=486 by ¹H NMR, Vinyls=97%, GPC        (M_(w)=874, M_(n)=499, M_(w)/M_(n)=1.75)    -   C₃C₄-VTM (Macromer B), M_(n)=1062 by ¹H NMR, Vinyls=95%, C₄=36        mol % by ¹³C NMR, GPC (M_(w)=2197, M_(n)=1030, M_(w)/M_(n)=2.13)    -   aPP-VTM (Macromer C), M_(n)=1866 by ¹H NMR, Vinyls=97%, GPC        (M_(w)=4789, M_(n)=2289, M_(w)/M_(n)=2.09)    -   C₂C₃-VTM (Macromer D), M_(n)=20831 by ¹H NMR, Vinyls=62%    -   C₃C₆-VTM (Macromer E), M_(n)=1567 by ¹H NMR, Vinyls=89%, C₆=46        mol % by ¹³C NMR, GPC (M_(w)=3143, M_(n)=1488, M_(w)/M_(n)=2.11)    -   aPP-VTM (Macromer F), M_(n)=1016 by ¹H NMR, Vinyls=92%, GPC        (M_(w)=2387, M_(n)=1069, M_(w)/M_(n), =2.23)    -   aPP-VTM (Macromer G), M_(n)=307 by ¹H NMR, Vinyls=97%, GPC        (M_(w)=290, M_(n)=285, M_(w)/M_(n)=1.02)    -   aPP-VTM (Macromer H), M_(n)=159 by ¹H NMR, Vinyls=97%, GPC        (M_(w)=184, M_(n)=175, M_(w)/M_(n)=1.05)    -   C₃C₆-VTM (Macromer I) M_(n)=2307 by ¹H NMR, vinyls=95%, C₆        content=43 mol % by ¹³C NMR    -   aPP-VTM (Macromer J) M_(n)=2108, Vinyls=97%    -   C₃C₄-VTM (Macromer K) M_(n)=2105 Vinyls=87.5%, C₄=47.6 mol % by        ¹³C NMR    -   C₃C₆-VTM (Macromer L) M_(n)=2215, Vinyls=82%, C₆ content 45.2        mol % by ¹³C NMR    -   C₃-VTM (Macromer M) M_(n)=1600, Vinyls=92%    -   HR-PIB (BASF Glissopal 1000), Vinylidene-80-85%, GPC        (M_(w)=1765, M_(n)=920, M_(w)/M_(n)=1.92)    -   Vinylidene aPP (Polymer N), M_(n)=2272 by ¹H NMR,        Vinylidene=95%, GPC (M_(w)=4475, M_(n)=2256, M_(w)/M_(n)=1.98)

Example 2 Preparation of Bromo-Terminated Atactic C₃ MacromerC₃—CH₂—CH₂—Br (1)

To a solution of vinyl-terminated atactic C₃ macromer A (M_(n) 486 g/molby ¹H NMR, 5.00 g, 10.29 mmol) in hexanes (4 ml) cooled to −10° C. wasadded dropwise 33 wt % hydrogen bromide solution in acetic acid (3.06ml, 16.8 mmol). After complete addition of the HBr solution, the mixturewas stirred at −10° C. for an additional 20 minutes. Ice-cold water (20ml) was added to the mixture and the aqueous phase was extracted withhexanes. The organic extract was washed with water (2×50 ml), dried overMgSO₄, filtered and concentrated on a rotary evaporator to give a lightyellow liquid product. The crude product was further purified by heatingat 60° C. to 65° C. under high vacuum to afford a clear liquid (5.73 g).¹H NMR supported the assignment of a primary bromide structure. ¹H NMR(400 MHz, CDCl₃): δ (ppm) 4.20 (—CHBrCH₃, br, 0.03 H, product 1b), 3.86(br, 0.03H) 3.39 (—CH ₂—Br, t, J=8.0 Hz, 2.0 H, product 1a), 1.87-1.78(—CH ₂CH₂—Br, m, 2.4H), 1.71-1.36 (m, 13.3H), 1.35-1.23 (m, 5.4H),1.23-0.94 (m, 19.9H), 0.94-0.5 (m, 44.2H). ¹³C NMR (100 MHz, CDCl₃): δ(ppm) 47.8-43.7 (m), 36.8-34.9 (m), 34.2 (—CH₂—Br, s), 30.5-29.4 (m,—CH₂CH₂—Br), 27.6-26.9 (m), 25.2-25.1 (m, —CH(CH₃)₂), 24.8-23.4 (m),22.6-21.9 (m), 21.5-19.0 (m). Elemental analysis: C, 72.78%; H, 12.58%;Br, 14.72%. GPC (M_(w)=809, M_(n)=473, M_(w)/M_(n)=1.71).

Example 3 Preparation of Bromo-Terminated C₃C₄ Macromer C₃C₄—CH₂—CH₂—Br(2)

To a solution of vinyl-terminated C₃C₄ macromer B (M_(n) 1062 g/mol by¹H NMR, 40.00 g, 37.66 mmol) in hexanes (50 ml) cooled to −10° C. wasadded dropwise a mixture of 33 wt % hydrogen bromide solution in aceticacid (13.18 ml, 72.5 mmol) and hexanes (10 ml) from an addition funnelover 15 min. After complete addition of the HBr solution, the mixturewas stirred between 0° C. to 10° C. for an additional 1.75 hours.Ice-cold water (100 ml) was added to the mixture and the aqueous phasewas extracted with hexanes (30 ml). The organic extract was washed withwater (2×150 ml), dried over MgSO₄, filtered and concentrated on arotary evaporator to give a clear and light yellow liquid product. Thecrude product was further purified by heating at 60° C. to 65° C. underhigh vacuum to afford a clear liquid (40.90 g). ¹H NMR supported theassignment of a primary bromide structure. ¹H NMR (400 MHz, CDCl₃): δ(ppm) 4.20 (—CHBrCH₃, br, 0.10 H, product 2b), 3.86 (br, 0.03 H) 3.39(—CH ₂—Br, t, J=8.0 Hz, 2.0 H, product 2a), 1.89-1.78 (—CH ₂CH₂—Br, m,2.3H), 1.73-1.48 (m, 14.8H), 1.48-1.22 (m, 26.0H), 1.22-0.91 (m, 44.3H),0.91-0.55 (m, 73.0H). ¹³C NMR (100 MHz, CDCl₃): δ (ppm) 47.9-43.7 (m),43.6-41.0 (m), 39.7-38.1 (m), 36.9-34.7 (m), 34.3-32.9 (m), 32.5-31.5(m), 30.8-28.9 (m), 27.4 (s), 27.0-25.2 (m), 23.9-22.1 (m), 21.6-19.0(m), 11.7-11.2 (m), 11.1-9.8 (m). Elemental analysis: C, 78.83%; H,13.39%; Br, 7.55%. GPC (M_(w)=2039, M_(n)=924, M_(w)/M_(n)=2.21). SeeFIG. 1 for the ¹H NMR spectrum of the product 2.

Example 4 Preparation of Bromo-Terminated Atactic C₃ MacromerC₃—CH₂—CH₂—Br (3)

To a solution of vinyl-terminated atactic C₃ macromer C (M_(n) 1866g/mol by ¹H NMR, 60.00 g, 32.16 mmol) in hexanes (50 ml) cooled to −10°C. was added dropwise a mixture of 33 wt % hydrogen bromide solution inacetic acid (11.25 ml, 61.9 mmol) and hexanes (10 ml) from an additionfunnel over 20 minutes. After complete addition of the HBr solution, themixture was stirred at −10° C. for an additional 20 minutes and then at0° C. for 1.5 hours. Ice-cold water (150 ml) was added to the mixtureand the aqueous phase was extracted with hexanes (80 ml). The organicextract was washed with water (2×150 ml), dried over MgSO₄, filtered andconcentrated on a rotary evaporator to give a clear and colorless liquidproduct. The crude product was further purified by heating at 60° C. to65° C. under high vacuum to afford a clear liquid (59.65 g). ¹H NMRsupported the assignment of a primary bromide structure. ¹H NMR (400MHz, CDCl₃): δ (ppm) 4.20 (—CHBrCH₃, br, 0.04 H, product 3b), 3.86 (br,0.01H) 3.39 (—CH ₂—Br, t, J=8.0 Hz, 2.0 H, product 3a), 1.95-1.79 (—CH₂CH₂—Br, m, 2.3H), 1.78-1.48 (m, 45.8H), 1.48-0.91 (m, 84.0H), 0.91-0.55(m, 146.8 H). ¹³C NMR (100 MHz, CDCl₃): δ (ppm) 48.0-43.8 (m), 36.8-36.2(m), 35.6-34.9 (m), 34.0 (—CH₂—Br, s), 30.7-30.4 (m), 29.7-29.5 (m),27.9-27.1 (m), 25.3-25.2 (m), 23.9-23.3 (m), 22.7-22.1 (m), 21.6-19.1(m). Elemental analysis: C, 82.06%; H, 13.84%; Br, 4.20%. GPC(M_(w)=4544, M_(n)=1978, M_(w)/M_(n)=2.30).

Example 5 Preparation of Bromo-Terminated C₂C₃ Macromer C₂C₃—CH₂—CH₂—Br(4)

To a solution of vinyl-terminated C₂C₃ macromer D (M_(n) 20831 g/mol by¹H NMR, 6.66 g, 0.32 mmol) in hexanes (45 ml) cooled to 0° C. was addeddropwise 33 wt % hydrogen bromide solution in acetic acid (0.256 ml,1.41 mmol) over 5 minutes. After complete addition of the HBr solution,the mixture was stirred between 0° C. to 10° C. for an additional 70minutes. Ice-cold water (40 ml) was added to the mixture and the aqueousphase was extracted with hexanes (25 ml). The organic extract was washedwith water (2×40 ml), dried over MgSO₄, filtered and concentrated on arotary evaporator to give a clear and light brown viscous liquidproduct. The crude product was further purified by heating at 60° C. to65° C. under high vacuum to afford a clear liquid (6.61 g). ¹H NMRsupported the assignment of a primary bromide structure. ¹H NMR (400MHz, CDCl₃): δ (ppm) 4.84 (br, 0.38H), 3.86 (m, 0.4H), 3.49-3.46 (m,0.4H) 3.39 (—CH ₂—Br, t, J=8.0 Hz, 2.0H), 1.95-1.80 (—CH ₂CH₂—Br, m,2.5H), 1.79-1.52 (br, 249.3H), 1.52-1.42 (br, 182.2H), 1.42-1.13 (br,1034.9H), 1.13-0.94 (m, 652.8H), 0.93-0.55 (1606.7H). ¹³C NMR (100 MHz,CDCl₃): δ (ppm) 47.4-44.0 (m), 38.8-37.8 (m), 37.8-36.5 (m), 32.8 (s),30.6-29.7 (m), 27.8-26.8 (m), 24.7-24.0 (m), 21.6-19.1 (m). Elementalanalysis: C, 84.79%; H, 14.21%; Br, 0.65%. GPC (M_(w)=37135,M_(n)=16547, M_(w)/M_(n)=2.24).

Example 6 Preparation of Bromo-Terminated C₃C₆ Macromer C₃C₆—CH₂—CH₂—Br(5)

To a solution of vinyl-terminated C₃C₆ macromer E (M_(n) 1567 g/mol by¹H NMR, 40.00 g, 25.52 mmol) in hexanes (50 ml) cooled to −10° C. wasadded dropwise a mixture of 33 wt % hydrogen bromide solution in aceticacid (8.93 ml, 49.1 mmol) and hexanes (10 ml) from an addition funnelover 40 min. After complete addition of the HBr solution, the mixturewas stirred between 0° C. to 10° C. for an additional 80 minutes.Ice-cold water (100 ml) was added to the mixture and the aqueous phasewas extracted with hexanes (60 ml). The organic extract was washed withwater (2×150 ml), dried over MgSO₄, filtered and concentrated on arotary evaporator to give a clear and pale yellow liquid product. Thecrude product was further purified by heating at 60° C. to 65° C. underhigh vacuum to afford a clear liquid (41.19 g). ¹H NMR supported theassignment of a primary bromide structure. ¹H NMR (400 MHz, CDCl₃): δ(ppm) 3.39 (—CH ₂—Br, t, J=8.0 Hz, 2.0H), 1.95-1.78 (—CH ₂ CH₂—Br, m,2.3H), 1.71-1.48 (m, 22.6H), 1.48-1.34 (br, 15.0H), 1.34-1.10 (m,98.5H), 1.10-0.96 (33.9H), 0.95-0.87 (53.5H), 0.87-0.55 (m, 48.2H). ¹³CNMR (100 MHz, CDCl₃): δ (ppm) 48.0-44.4 (m), 44.2-41.7 (m), 40.7-39.2(m), 35.0-32.8 (m), 32.8-31.8 (m), 30.7-29.1 (m), 29.1-27.9 (m),27.9-27.2 (m), 23.7-22.8 (m), 21.6-19.1 (m), 14.3 (s). Elementalanalysis: C, 80.65%; H, 13.66%; Br, 5.38%. GPC (M_(w)=3004, M_(n)=1407,M_(w)/M_(n)=2.14).

Example 7 Preparation of Bromo-Terminated Atactic C₃ MacromerC₃—CH₂—CH₂—Br (6)

To a solution of vinyl-terminated atactic C₃ macromer F (M_(n) 1016g/mol by ¹H NMR, 91.74 g, 90.32 mmol) in hexanes (130 ml) cooled to 0°C. was added dropwise a mixture of 33 wt % hydrogen bromide solution inacetic acid (28.90 ml, 159.0 mmol) and hexanes (20 ml) from an additionfunnel over 30 minutes. After complete addition of the HBr solution, themixture was stirred at 0° C. for an additional 75 minutes. Ice-coldwater (300 ml) was added to the mixture and the aqueous phase wasextracted with hexanes (150 ml). The organic extract was washed withwater (2×250 ml), dried over MgSO₄, filtered and concentrated on arotary evaporator to give a clear and pale yellow liquid product. Thecrude product was further purified by heating at 60° C. to 65° C. underhigh vacuum to afford a clear liquid (96.13 g). ¹H NMR supported theassignment of a primary bromide structure. ¹H NMR (400 MHz, CDCl₃): δ(ppm) 4.20 (—CHBrCH₃, br, 0.06 H, product 6b), 4.00 (br, 0.06H), 3.86(br, 0.06H) 3.39 (—CH ₂—Br, t, J=8.0 Hz, 2.0 H, product 6a), 2.09-2.15(br, 0.06 H), 1.95-1.76 (—CH ₂CH₂—Br, m, 2.5H), 1.76-1.33 (m, 26.8H),1.33-0.91 (m, 45.7H), 0.91-0.62 (m, 79.8H). ¹³C NMR (100 MHz, CDCl₃): δ(ppm) 48.0-42.5 (m), 36.8-36.2 (m), 35.6-35.0 (m), 34.0, 33.8 (—CH₂—Br,s), 30.7-30.4 (m), 30.3-29.7 (m), 29.7-29.5 (m), 27.9-27.1 (m),25.3-25.2 (m), 23.9-23.3 (m), 22.7-22.1 (m), 21.6-19.2 (m). Elementalanalysis: C, 78.80%; H, 13.34%; Br, 7.51%. GPC (M_(w)=2228, M_(n)=994,M_(w)/M_(n)=2.24).

Example 8 Preparation of Bromo-Terminated Atactic C₃ MacromerC₃—CH₂—CH₂—Br (7) from Atactic C₃ Distilled Fraction Macromer G(Polydispersity Index, Mw/Mn=1.02)

To a solution of vinyl-terminated atactic C₃ distilled fraction macromerG (M_(n) 307 g/mol by ¹H NMR, 6.0 g, 19.56 mmol) in hexanes (9 ml)cooled to −10° C. was added dropwise 33 wt % hydrogen bromide solutionin acetic acid (5.53 ml, 30.4 mmol). After complete addition of the HBrsolution, the mixture was stirred between −10° C. and −8° C. for anadditional 30 minutes. Ice-cold water (60 ml) was added to the mixtureand the aqueous phase was extracted with hexanes (30 ml). The combinedorganic extract was washed with water, aqueous sodium carbonatesolution, brine, dried over MgSO₄, filtered and concentrated on a rotaryevaporator to give a clear and light yellow liquid product (7.45 g). ¹HNMR supported the assignment of a primary bromide structure. ¹H NMR (400MHz, CDCl₃): δ (ppm) 4.20 (—CHBrCH₃, br, 0.05 H, product 7b), 4.00 (br,0.04H), 3.86 (br, 0.04 H), 3.39 (—CH ₂—Br, t, J=8.0 Hz, 2.0 H, product7a), 1.95-1.75 (—CH ₂CH₂—Br, m, 2.3H), 1.75-1.49 (m, 6.0H), 1.49-1.31(m, 2.1H), 1.31-0.91 (m, 12.0H), 0.91-0.62 (m, 23.2H). ¹³C NMR (100 MHz,CDCl₃): δ (ppm) 47.9-41.8 (m), 36.6-36.0 (m), 35.8-34.9 (m), 34.2 (s),34.1 (—CH₂—Br, s), 33.2-31.5 (m), 30.6-29.4 (m), 27.8-27.0 (m),25.3-25.1 (m), 23.9-21.9 (m), 21.3-19.2 (m). Elemental analysis: C,65.42%; H, 11.37%; Br: 22.81%.

Preparation of Bromo-Terminated Atactic C₃ Macromer C₃—CH₂—CH₂—Br (8)from Atactic C₃ Distilled Fraction Macromer H (Polydispersity Index,Mw/Mn=1.05)

To a solution of vinyl-terminated atactic C₃ distilled fraction macromerH (M_(n) 159 g/mol by ¹H NMR, 4.0 g, 25.11 mmol) in hexanes (12 ml)cooled to −10° C. was added dropwise 33 wt % hydrogen bromide solutionin acetic acid (6.82 ml, 37.5 mmol). After complete addition of the HBrsolution, the mixture was stirred between −10° C. and −8° C. for anadditional 30 minutes. Ice-cold water (80 ml) was added to the mixtureand the aqueous phase was extracted with hexanes. The combined organicextract was washed with water, aqueous sodium carbonate solution, brine,dried over MgSO₄, filtered and concentrated on a rotary evaporator togive a clear and light yellow liquid product (5.46 g). ¹H NMR supportedthe assignment of a primary bromide structure. ¹H NMR (400 MHz, CDCl₃):δ (ppm) 4.20 (—CHBrCH₃, br, 0.04 H, product 8b), 4.00 (br, 0.03H), 3.86(br, 0.02H) 3.39 (—CH ₂—Br, t, J=8.0 Hz, 2.0 H, product 8a), 1.95-1.75(—CH ₂CH₂—Br, m, 2.2H), 1.75-1.59 (m, 1.3H), 1.59-1.46 (m, 1.7H),1.46-1.31 (m, 1.2H), 1.31-1.16 (m, 1.3H), 1.16-0.92 (3.3H), 0.91-0.62(m, 11.8H). ¹³C NMR (100 MHz, CDCl₃): δ (ppm) 47.53 (s), 46.66 (s),46.54 (s), 45.82 (s), 45.45 (s), 45.42 (s), 44.88 (s), 44.77 (s), 43.98(s), 36.32 (s), 35.78 (s), 35.23 (s), 34.22 (s), 34.05 (—CH₂—Br, s),30.49 (s), 30.42 (s), 30.36 (s), 29.72 (s), 29.65 (s), 29.53 (s), 29.46(s), 29.42 (s), 29.36 (s), 27.55 (s), 27.50 (s), 27.43 (s), 27.4-27.2(m), 25.15 (s), 25.08 (s), 23.66 (s), 23.63 (s), 23.38 (s), 23.32 (s),23.23 (s), 23.17 (s), 23.05 (s), 22.74 (s), 22.48 (s), 22.45 (s), 22.39(s), 22.32 (s), 22.23 (s), 22.11 (s), 22.05 (s), 20.32 (s), 20.16 (s),20.12 (s), 20.08-20.06 (m), 19.65 (s), 19.50 (s), 19.37 (s). Elementalanalysis: C, 54.66%; H, 9.52%; Br: 35.85%.

Example 10 Preparation of Bromo-Terminated Atactic C₃ MacromerC₃—CH₂—CH₂—Br (9)

To a solution of vinyl-terminated atactic C₃ macromer A (M_(n) 486 g/molby ¹H NMR, 5.00 g, 10.29 mmol) in hexanes (4 ml) at 25° C. was addeddropwise 33 wt % hydrogen bromide solution in acetic acid (2.79 ml, 15.3mmol). After complete addition of the HBr solution, the mixture wasstirred at 25° C. for an additional 20 minutes. Water (20 ml) was addedto the mixture at 25° C. and the aqueous phase was extracted withhexanes. The combined organic extract was washed with water, aqueoussodium carbonate solution, brine, dried over MgSO₄, filtered andconcentrated on a rotary evaporator to give a clear and colorless liquidproduct (5.54 g). ¹H NMR supported the assignment of a primary bromidestructure. ¹H NMR (400 MHz, CDCl₃): δ (ppm) 4.20 (—CHBrCH₃, br, 0.08 H,product 9b), 3.86 (br, 0.08H) 3.39 (—CH ₂—Br, t, J=8.0 Hz, 2.0 H,product 9a), 1.95-1.77 (—CH ₂CH₂—Br, m, 2.4H), 1.76-1.32 (m, 13.9H),1.39-0.90 (m, 21.2H), 0.90-0.55 (m, 41.1H). ¹³C NMR (100 MHz, CDCl₃): δ(ppm) 48.0-43.7 (m), 36.8-36.4 (m), 36.3-36.1 (m), 35.7-35.3 (m),35.2-34.9 (m), 33.9 (—CH₂—Br, s), 30.7-30.4 (m), 29.7-29.4 (m),27.8-27.0 (m), 25.3-25.2 (m), 24.9-23.3 (m), 22.6-22.0 (m), 21.6-19.1(m). Elemental analysis: C, 72.71%; H, 12.42%; Br, 15.00%.

Example 11 Preparation of C₃C₆—Br (10)

C₃C₆-VTM macromer I (M_(n)=2307, 40.4 g) was dissolved in hexane (60 ml)and cooled to 0° C. A solution of HBr (7.0 ml, 33 wt % in acetic acid)was slowly added during a 15 minute time interval. An aliquot at 3 hoursof reaction time indicated that all vinyl end groups were consumed. Thereaction mixture was transferred to a separatory funnel and washed withH₂O (3×100 ml). The volatiles were removed from the organic layer andthe product dried in a vacuum oven at 80° C. for 12 hours (38.0 g). ¹HNMR (500 MHz, CDCl₃): δ (ppm) 3.46 (t, 1H), 2.0-0.5 (m, 211.7H). ¹³C NMR(125 MHz, CDCl₃): δ (ppm) 34.4 (—CH₂—Br, s, overlaps with otherresonances) 30.8 (m, —CH₂CH₂—Br, 1.0 C), 25.6 (m, —CH (CH₃)₂, 1.2 C).

Example 12 Preparation of aPP-Br (11)

aPP-VTM macromer J (M_(n)=2108, 91 g) was dissolved in hexane (100 ml)and cooled to 0° C. A solution of HBr (17 ml, 33 wt % in acetic acid)was added by addition funnel over a 30 minute time period. An aliquot at2 hours of reaction time indicated the disappearance of all vinyl chainends. The crude reaction was washed with H₂O (3×200 ml) and volatileswere removed. The product was dried in a vacuum oven at 70° C. for 12hours. A foaming problem occurred while drying this particular productwhich resulted in a reduced yield (65.4 g). ¹H NMR (500 MHz, CDCl₃): δ(ppm) 3.35 (m, —CH ₂—Br, 1.0H), 1.87 (m, —CH ₂—CH₂—Br, 0.91H), 1.76-0.40(m, 164.9H). There are additional peaks at 4.18 (0.02H) and 3.94 (m,0.01H) most likely due to addition of HBr to form secondary bromide. ¹³CNMR (125 MHz, CDCl₃): δ (ppm) 34.0 (—CH₂—Br, s, 1.0 C), 30.9 (m,—CH₂—CH₂—Br, 0.90 C), 25.45 (m, —CH(CH₃)₂, 1.10 C). Elemental analysis:C, 81.4%; H, 13.7%; Br, 2.4%.

Example 13 Preparation of C₃C₄—Br (12)

Similarly, this product was prepared with C₃C₄-VTM macromer K(M_(n)=2105, 76 g) and HBr solution (14.3 ml, 33 wt % in acetic acid)for a yield of 40.3 g. Some loss of product occurred while drying.

Example 14 Preparation of C₃C₆—Br (13)

Similarly, this product was prepared with C₃C₆-VTM macromer L(M_(n)=2215, 114.5 g,) and HBr solution (20.3 ml, 33 wt % in aceticacid) for a yield of 96.3 g. ¹H NMR (500 MHz, CDCl₃): δ (ppm) 3.37 (t,—CH₂—Br, 1H), 2.25-0.5 (m, 275.1H).

Example 15 Preparation of C₃C₆—Br (14)

Similarly, this product was prepared with C₃C₆-VTM macromer L(M_(n)=2215, 54.2 g) and HBr solution (10 ml, 33 wt % in acetic acid)for a yield of 41.2 g. ¹H NMR (500 MHz, CDCl₃): δ (ppm) 3.37 (t, 1H),2.25-0.5 (m, 275.1H).

Example 16 Preparation of C₃—Br (15)

Similarly, this product was prepared with C₃-VTM macromer M (M_(n)=1600,136 g,) and HBr solution (34 ml, 33 wt % in acetic acid) for a yield of132.5 g. ¹H NMR (500 MHz, CDCl₃): δ (ppm) 4.1 (br s, 0.02H) and 3.9-3.75(m, 0.03H), 3.22 (t, 1H), 2.25-0.5 (m, 154.1H).

Example 17 Preparation of Bromo-Terminated Polyisobutylene (16) fromHighly Reactive Polyisobutylene (Glissopal 1000)

To a solution of predominately vinylidene-terminated polyisobutylene(Glissopal 1000 from BASF, 50.00 g) in hexanes (50 ml) cooled to −8° C.was added dropwise a mixture of 33 wt % hydrogen bromide solution inacetic acid (18.62 ml, 93.1 mmol) and hexanes (10 ml) from an additionfunnel over 15 minutes. After complete addition of the HBr solution, themixture was stirred at between −8° C. to 0° C. for an additional 1.5hours. Ice-cold water (150 ml) was added to the mixture and the aqueousphase was extracted with hexanes (80 ml). The organic extract was washedwith water (2×200 ml), dried over MgSO₄, filtered and concentrated on arotary evaporator to give a clear and pale yellow liquid as crudeproduct. The crude product was further purified by heating at 60° C. to65° C. under high vacuum to afford a clear liquid (52.20 g). ¹H NMR (400MHz, CDCl₃): δ (ppm) 4.04-4.03 (m, 0.1H), 3.42-3.39 (dd, 1.0H),3.29-3.25 (dd, 1.0H), 1.97-1.85 (m, 1.3H), 1.84-1.63 (br, 1.0H),1.61-1.51 (m, 2.7H), 1.49-1.36 (m, 36.0H), 1.36-1.29 (br, 5.6H),1.29-1.05 (m, 119.3H), 1.04-0.94 (m, 22.9H), 0.94-0.73 (m, 1.8H). ¹³CNMR (100 MHz, CDCl₃): δ (ppm) 59.5 (s), 59.4-59.3 (m), 58.89 (s), 58.28(s), 56.83 (s), 51.23 (s), 43.41 (s), 38.20 (s), 38.14 (s), 37.93 (s),37.83 (s), 35.90 (s), 32.64 (s), 32.59 (s), 32.54 (s), 31.62 (s), 31.37(s), 31.30 (s), 31.17 (s), 30.92 (s), 29.32 (s), 29.15 (s), 22.16 (s).Elemental analysis: C, 79.59%; H, 13.17%; Br, 7.39%. GPC (M_(w)=1691,M_(n)=909, M_(w)/M_(n)=1.86).

Example 18 Preparation of Bromo-Terminated Atactic Polypropylene (17)from Vinylidene-Terminated Polypropylene N

To a solution of vinylidene-terminated atactic polypropylene N (M_(n)2272 g/mol by ¹H NMR, 6.85 g, 3.02 mmol) in hexanes (24 ml) cooled to 0°C. was added dropwise 33 wt % hydrogen bromide solution in acetic acid(1.06 ml, 5.3 mmol) over 3 minutes. After complete addition of the HBrsolution, the mixture was stirred at 0° C. for 30 minutes and then at 5°C. for 2 hours. Ice-cold water (65 ml) was added to the mixture and theaqueous phase was extracted with hexanes (10 ml). The combined organicextract was washed with water (75 ml) and half-saturated brine (10 ml),dried over MgSO₄, filtered and concentrated on a rotary evaporator togive a slightly cloudy and pale yellow liquid as crude product (6.84 g).¹H NMR (400 MHz, CDCl₃): δ (ppm) 3.87 (br, 0.1H), 3.80 (br, 0.08H),3.53-3.26 (m, 2.0 H), 2.17-1.82 (m, 2.0H), 1.82-1.42 (m, 57.0H),1.42-1.23 (m, 31.1H), 1.23-0.52 (m, 276.8 H). ¹³C NMR (100 MHz, CDCl₃):δ (ppm) 47.5-43.2 (m), 42.8-42.2 (m), 42.0-41.8 (m), 41.5-41.2 (m),40.8-40.2 (m), 39.6-38.8 (m), 33.1-32.7 (m), 32.5-32.3 (m), 27.8-27.2(m), 21.6-19.2 (m), 14.6-14.5 (m). Elemental analysis: C, 80.95%; H,13.73%; Br, 4.17%. GPC (M_(w)=4294, M_(n)=2095, M_(w)/M_(w)=2.05).

Example 19 Reaction of C₃-Vinylidene with HBr (18)

C₃-Vinylidene N (15.5 g) was dissolved in hexane (100 ml) and cooled to0° C. A solution of HBr (6.8 ml, 33 wt % in acetic acid) was added over15 minutes. The reaction was stirred and warmed to ambient temperaturesover 2.5 hours and the reaction mixture subjected to the usual aqueouswork-up as described above. The product was dried in a vacuum oven at70° C. for 12 hours (14.5 g). ¹H NMR (500 MHz, CDCl₃): δ (ppm) 3.6-3.0(m, 1.0H), 2.5-0.5 (m, 168.8H). There are additional peaks at 4.72 to4.5 (m, 0.03H) and 4.15 to 3.85 (m, 0.17H).

Comparative Examples Example 20 Reaction of C₃C₄-Bromide withPhthalimide (19)

A mixture of potassium phthalimide (0.875 g, 4.72 mmol) andbromo-terminated C₃C₄ macromer 2 (from Example 3, 2.50 g, 2.36 mmol ofBr) in N,N-dimethylformamide (9 ml) and tetrahydrofuran (18 ml) washeated at 80° C. (oil bath) for 13 hours under a nitrogen atmosphere.The mixture was cooled to 25° C., filtered and the solvent was removedin vacuo. The residue was dissolved in hexanes, washed with water,brine, dried over MgSO₄, filtered and concentrated on a rotaryevaporator to give a pale yellow oil product (2.60 g). ¹H NMR indicatedconsumption of the primary bromide. Elemental analysis: C, 82.62%; H,13.23%; N, 1.16%; Br, <0.25%.

Example 21 Reaction of C₃C₄-Bromide with Potassium Hydroxide (20)

To a solution of bromo-terminated C₃C₄ macromer 2 (from Example 3, 3.79g, 3.58 mmol of Br) in tetrahydrofuran (18 ml) and1-methyl-2-pyrrolidinone (9 ml) at 25° C. was added a solution of KOH(1.61 g, 28.65 mmol) in water (2 ml). The mixture was heated at 70° C.for 20 hours. The mixture was cooled to 25° C. and the aqueous phase wasextracted with hexanes (25 ml). The organic extract was washed withwater (2×45 ml), dried over MgSO₄, filtered and concentrated on a rotaryevaporator to give a light yellow viscous oil as crude product (3.68 g).¹H NMR (400 MHz, CDCl₃) indicated consumption of the primary bromide.Elemental analyses found C, 77.89%, H, 13.34%.

Example 22 Reaction of C₃C₄-Bromide with N-Hydroxyphthalimide (21)

A mixture of N-hydroxyphthalimide (0.475 g, 2.91 mmol) and potassiumcarbonate (0.575 g, 4.16 mmol) in N,N-dimethylformamide (8 ml) washeated to 80° C. for 10 minutes. To this brown mixture was added asolution of bromo-terminated C₃C₄ macromer 2 (from Example 3, 2.20 g,2.08 mmol of Br) in tetrahydrofuran (20 ml) and the resulting mixturewas heated at 80° C. (oil bath) for 19 hours under a nitrogenatmosphere. The mixture was cooled to 25° C., filtered and the solventwas removed in vacuo. The residue was dissolved in hexanes, washed withwater, brine, dried over MgSO₄, filtered and concentrated on a rotaryevaporator to give a clear yellow oil product (2.10 g). ¹H NMR indicatedconsumption of the primary bromide. ¹H NMR (400 MHz, CDCl₃): δ (ppm)7.85-7.82 (m, 2.0H), 7.75-7.73 (m, 2.0H), 4.19 (—CH ₂—O—N, t, 2.0H),1.93-1.72 (br, 2.5H), 1.72-1.47 (m, 18.0H), 1.47-1.22 (m, 39.0H),1.22-0.92 (m, 48.3H), 0.92-0.55 (m, 92.5H).

Example 23 Reaction of C₃C₆-Bromide with 4-Fluorophenol (22)

A mixture of 4-fluorophenol (0.434 g, 3.87 mmol), potassium carbonate(0.745 g, 5.39 mmol), potassium iodide (0.056 g, 0.337 mmol) andbromo-terminated C₃C₆ macromer 5 (from Example 6, 5.00 g, 3.37 mmol ofBr) in tetrahydrofuran (20 ml) and 1-methyl-2-pyrrolidinone (10 ml) washeated at 85° C. to 95° C. (oil bath) overnight under a nitrogenatmosphere. The mixture was cooled to 25° C. and the solvent was removedin vacuo. The residue was dissolved in hexanes, washed with water,brine, dried over MgSO₄, filtered and concentrated on a rotaryevaporator to give a light yellow viscous oil product (4.88 g). ¹H NMRindicated consumption of the primary bromide. ¹H NMR (400 MHz, CDCl₃): δ(ppm) 6.97-6.93 (m, 2.2H), 6.83-6.80 (m, 2.1H), 3.89 (—CH ₂—O, t, 2.0H),2.07-1.67 (br, 3.3H), 1.67-1.48 (m, 22.6H), 1.48-1.34 (m, 16.6H),1.34-1.16 (m, 94.9H), 1.16-0.93 (m, 57.1H), 0.93-0.86 (m, 59.2H),0.86-0.55 (m, 55.5H). Elemental analysis: C, 84.70%; H, 14.23%; F,0.68%; Br, trace <0.25%.

Example 24 Reaction of C₃—Br with Cyclopentadienyl Lithium (CpLi) (23)

C₃—Br (from Example 16, 29.4 g) was dissolved in THF (100 ml) and driedover 3 A sieves for 48 hours. The solution was decanted into a roundbottom glass flask with stir bar and 1.3 g (CpLi, Strem) was added. Thereaction mixture was refluxed under a N₂ atmosphere overnight. Thereaction was cooled to ambient temperature and an additional 1.3 g ofCpLi was added. The reaction mixture was stirred for 48 hours. Analiquot analyzed by ¹H NMR indicated that all CH₂—Br groups had beenconsumed. The reaction mixture was diluted with hexane (90 ml) andwashed with H₂O (3×100 ml). The volatiles were removed and the productdried in a vacuum oven at 70° C. for 12 hours. ¹H NMR (500 MHz, CDCl₃):δ (ppm) 6.3-5.55 (m, 1.0H), 2.8-2.65 (m, 0.8H), 2.65-2.1 (m, 1.9H),2.0-0.5 (m, 118.2H).

All documents described herein are incorporated by reference herein,including any priority documents and/or testing procedures to the extentthey are not inconsistent with this text, provided however that anypriority document not named in the initially filed application or filingdocuments is NOT incorporated by reference herein. As is apparent fromthe foregoing general description and the specific embodiments, whileforms of the invention have been illustrated and described, variousmodifications can be made without departing from the spirit and scope ofthe invention. Accordingly, it is not intended that the invention belimited thereby. Likewise, the term “comprising” is consideredsynonymous with the term “including” for purposes of Australian law.Likewise whenever a composition, an element or a group of elements ispreceded with the transitional phrase “comprising”, it is understoodthat we also contemplate the same composition or group of elements withtransitional phrases “consisting essentially of,” “consisting of”,“selected from the group of consisting of,” or “is” preceding therecitation of the composition, element, or elements and vice versa.Thus, the term “comprising” encompasses the terms “consistingessentially of,” “is,” and “consisting of” and anyplace “comprising” isused “consisting essentially of,” “is,” or consisting of may besubstituted therefor.

What is claimed is:
 1. A polyolefin composition comprising one or moreof the following formulae:

wherein the PO is the residual portion of a vinyl terminatedmacromonomer (VTM) having had a terminal unsaturated carbon of anallylic chain and a vinyl carbon adjacent to the terminal unsaturatedcarbon; X is attached to the terminal portion of the VTM to provide PO—Xor at the vinylidene carbon of the VTM to provide PO—CHXCH₃; and X isCl, Br, I, or F.
 2. The polyolefin composition of claim 1, wherein theVTM is one or more of: (i) a vinyl terminated polymer having at least 5%allyl chain ends; (ii) a vinyl terminated polymer having an Mn of atleast 160 g/mol (measured by ¹H NMR) comprising of one or more C₄ to C₄₀higher olefin derived units, where the higher olefin polymer comprisessubstantially no propylene derived units; and wherein the higher olefinpolymer has at least 5% allyl chain ends; (iii) a copolymer having an Mnof 300 g/mol or more (measured by ¹H NMR) comprising (a) from about 20mol % to about 99.9 mol % of at least one C₅ to C₄₀ higher olefin, and(b) from about 0.1 mol % to about 80 mol % of propylene, wherein thehigher olefin copolymer has at least 40% allyl chain ends; (iv) acopolymer having an Mn of 300 g/mol or more (measured by ¹H NMR), andcomprises (a) from about 80 mol % to about 99.9 mol % of at least one C₄olefin, (b) from about 0.1 mol % to about 20 mol % of propylene; andwherein the vinyl terminated macromonomer has at least 40% allyl chainends relative to total unsaturation; (v) a co-oligomer having an Mn of300 g/mol to 30,000 g/mol (measured by ¹H NMR) comprising 10 mol % to 90mol % propylene and 10 mol % to 90 mol % of ethylene, wherein theoligomer has at least X % allyl chain ends (relative to totalunsaturations), where: 1) X=(−0.94*(mol % ethylene incorporated)+100),when 10 mol % to 60 mol % ethylene is present in the co-oligomer, 2)X=45, when greater than 60 mol % and less than 70 mol % ethylene ispresent in the co-oligomer, and 3) X=(1.83*(mol % ethyleneincorporated)−83), when 70 mol % to 90 mol % ethylene is present in theco-oligomer; (vi) a propylene oligomer, comprising more than 90 mol %propylene and less than 10 mol % ethylene wherein the oligomer has: atleast 93% allyl chain ends, a number average molecular weight (Mn) ofabout 500 g/mol to about 20,000 g/mol, an isobutyl chain end to allylicvinyl group ratio of 0.8:1 to 1.35:1.0, less than 100 ppm aluminum,and/or less than 250 regio defects per 10,000 monomer units; (vii) apropylene oligomer, comprising: at least 50 mol % propylene and from 10mol % to 50 mol % ethylene, wherein the oligomer has: at least 90% allylchain ends, an Mn of about 150 g/mol to about 20,000 g/mol, and anisobutyl chain end to allylic vinyl group ratio of 0.8:1 to 1.2:1.0,wherein monomers having four or more carbon atoms are present at from 0mol % to 3 mol %; (viii) a propylene oligomer, comprising: at least 50mol % propylene, from 0.1 mol % to 45 mol % ethylene, and from 0.1 mol %to 5 mol % C₄ to C₁₂ olefin, wherein the oligomer has: at least 90%allyl chain ends, an Mn of about 150 g/mol to about 10,000 g/mol, and anisobutyl chain end to allylic vinyl group ratio of 0.8:1 to 1.35:1.0;(ix) a propylene oligomer, comprising: at least 50 mol % propylene, from0.1 mol % to 45 mol % ethylene, and from 0.1 mol % to 5 mol % diene,wherein the oligomer has: at least 90% allyl chain ends, an Mn of about150 g/mol to about 10,000 g/mol, and an isobutyl chain end to allylicvinyl group ratio of 0.7:1 to 1.35:1.0; (x) a homo-oligomer, comprisingpropylene, wherein the oligomer has: at least 93% allyl chain ends, anMn of about 500 g/mol to about 70,000 g/mol, an isobutyl chain end toallylic vinyl group ratio of 0.8:1 to 1.2:1.0, and less than 1400 ppmaluminum; (xi) vinyl terminated polyethylene having: (a) at least 60%allyl chain ends; (b) a molecular weight distribution of less than orequal to 4.0; (c) a g′(_(vis)) of greater than 0.95; and (d) an Mn (¹HNMR) of at least 20,000 g/mol; and (xii) vinyl terminated polyethylenehaving: (a) at least 50% allyl chain ends; (b) a molecular weightdistribution of less than or equal to 4.0; (c) a g′(_(vis)) of 0.95 orless; (d) an Mn (¹H NMR) of at least 7,000 g/mol; and (e) a Mn (GPC)/Mn(¹H NMR) in the range of from about 0.8 to about 1.2.
 3. A polyolefincomposition comprising one or more of the following formulae:

wherein the PO is the residual portion of a vinyl terminatedmacromonomer (VTM) having had a terminal unsaturated carbon of anallylic chain and a vinyl carbon adjacent to the terminal unsaturatedcarbon; Y is a hydroxyl, an ether group, a cyano, a C₁-C₂₀ alkyl group,a cyclopentadienyl, an aromatic group, or a phthalimide group.
 4. Thepolyolefin of claim 3, wherein the VTM is one or more of: (i) a vinylterminated polymer having at least 5% allyl chain ends; (ii) a vinylterminated polymer having an Mn of at least 160 g/mol (measured by ¹HNMR) comprising of one or more C₄ to C₄₀ higher olefin derived units,where the higher olefin polymer comprises substantially no propylenederived units; and wherein the higher olefin polymer has at least 5%allyl chain ends; (iii) a copolymer having an Mn of 300 g/mol or more(measured by ¹H NMR) comprising (a) from about 20 mol % to about 99.9mol % of at least one C₅ to C₄₀ higher olefin, and (b) from about 0.1mol % to about 80 mol % of propylene, wherein the higher olefincopolymer has at least 40% allyl chain ends; (iv) a copolymer having anMn of 300 g/mol or more (measured by ¹H NMR), and comprises (a) fromabout 80 mol % to about 99.9 mol % of at least one C₄ olefin, (b) fromabout 0.1 mol % to about 20 mol % of propylene; and wherein the vinylterminated macromonomer has at least 40% allyl chain ends relative tototal unsaturation; (v) a co-oligomer having an Mn of 300 g/mol to30,000 g/mol (measured by ¹H NMR) comprising 10 mol % to 90 mol %propylene and 10 mol % to 90 mol % of ethylene, wherein the oligomer hasat least X % allyl chain ends (relative to total unsaturations),where: 1) X=(−0.94*(mol % ethylene incorporated)+100), when 10 mol % to60 mol % ethylene is present in the co-oligomer, 2) X=45, when greaterthan 60 mol % and less than 70 mol % ethylene is present in theco-oligomer, and 3) X=(1.83*(mol % ethylene incorporated)−83), when 70mol % to 90 mol % ethylene is present in the co-oligomer; (vi) apropylene oligomer, comprising more than 90 mol % propylene and lessthan 10 mol % ethylene wherein the oligomer has: at least 93% allylchain ends, a number average molecular weight (Mn) of about 500 g/mol toabout 20,000 g/mol, an isobutyl chain end to allylic vinyl group ratioof 0.8:1 to 1.35:1.0, less than 100 ppm aluminum, and/or less than 250regio defects per 10,000 monomer units; (vii) a propylene oligomer,comprising: at least 50 mol % propylene and from 10 mol % to 50 mol %ethylene, wherein the oligomer has: at least 90% allyl chain ends, an Mnof about 150 g/mol to about 20,000 g/mol, and an isobutyl chain end toallylic vinyl group ratio of 0.8:1 to 1.2:1.0, wherein monomers havingfour or more carbon atoms are present at from 0 mol % to 3 mol %; (viii)a propylene oligomer, comprising: at least 50 mol % propylene, from 0.1mol % to 45 mol % ethylene, and from 0.1 mol % to 5 mol % C₄ to C₁₂olefin, wherein the oligomer has: at least 90% allyl chain ends, an Mnof about 150 g/mol to about 10,000 g/mol, and an isobutyl chain end toallylic vinyl group ratio of 0.8:1 to 1.35:1.0; (ix) a propyleneoligomer, comprising: at least 50 mol % propylene, from 0.1 mol % to 45mol % ethylene, and from 0.1 mol % to 5 mol % diene, wherein theoligomer has: at least 90% allyl chain ends, an Mn of about 150 g/mol toabout 10,000 g/mol, and an isobutyl chain end to allylic vinyl groupratio of 0.7:1 to 1.35:1.0; (x) a homo-oligomer, comprising propylene,wherein the oligomer has: at least 93% allyl chain ends, an Mn of about500 g/mol to about 70,000 g/mol, an isobutyl chain end to allylic vinylgroup ratio of 0.8:1 to 1.2:1.0, and less than 1400 ppm aluminum; (xi)vinyl terminated polyethylene having: (a) at least 60% allyl chain ends;(b) a molecular weight distribution of less than or equal to 4.0; (c) ag′(_(vis)) of greater than 0.95; and (d) an Mn (¹H NMR) of at least20,000 g/mol; and (xii) vinyl terminated polyethylene having: (a) atleast 50% allyl chain ends; (b) a molecular weight distribution of lessthan or equal to 4.0; (c) a g′(_(vis)) of 0.95 or less; (d) an Mn (¹HNMR) of at least 7,000 g/mol; and (e) a Mn (GPC)/Mn (¹H NMR) in therange of from about 0.8 to about 1.2.
 5. The polyolefin composition ofclaim 3, wherein the ether group comprises the formula:—OR₁—O—R₂_(n)R₉, wherein R₁ is an alkyl or an aryl; R₂ is a bond, analkyl or an aryl; R₉ is an alkyl or an aryl; and n is from 1 to about500.
 6. The polyolefin composition of claim 3, wherein the ether groupcomprises the formula:—OR₁—O—R₄_(n)OR₈, wherein each R₁ and R₄ is, independently, an alkylor an aryl; R₈ is an alkyl or an aryl; and n is from 1 to about
 500. 7.The polyolefin compositions of claim 1, wherein the composition isamorphous.
 8. A method to functionalize a vinyl terminated macromonomer(VTM) comprising the step: contacting a VTM with a compound having theformula HX, wherein X is Cl, I, Br, or F to provide an X functionalizedVTM.
 9. The method of claim 8, wherein the VTM is one or more of: (i) avinyl terminated polymer having at least 5% allyl chain ends; (ii) avinyl terminated polymer having an Mn of at least 160 g/mol (measured by¹H NMR) comprising of one or more C₄ to C₄₀ higher olefin derived units,where the higher olefin polymer comprises substantially no propylenederived units; and wherein the higher olefin polymer has at least 5%allyl chain ends; (iii) a copolymer having an Mn of 300 g/mol or more(measured by ¹H NMR) comprising (a) from about 20 mol % to about 99.9mol % of at least one C₅ to C₄₀ higher olefin, and (b) from about 0.1mol % to about 80 mol % of propylene, wherein the higher olefincopolymer has at least 40% allyl chain ends; (iv) a copolymer having anMn of 300 g/mol or more (measured by ¹H NMR), and comprises (a) fromabout 80 mol % to about 99.9 mol % of at least one C₄ olefin, (b) fromabout 0.1 mol % to about 20 mol % of propylene; and wherein the vinylterminated macromonomer has at least 40% allyl chain ends relative tototal unsaturation; (v) a co-oligomer having an Mn of 300 g/mol to30,000 g/mol (measured by ¹H NMR) comprising 10 mol % to 90 mol %propylene and 10 mol % to 90 mol % of ethylene, wherein the oligomer hasat least X % allyl chain ends (relative to total unsaturations),where: 1) X=(−0.94*(mol % ethylene incorporated)+100), when 10 mol % to60 mol % ethylene is present in the co-oligomer, 2) X=45, when greaterthan 60 mol % and less than 70 mol % ethylene is present in theco-oligomer, and 3) X=(1.83*(mol % ethylene incorporated)−83), when 70mol % to 90 mol % ethylene is present in the co-oligomer; (vi) apropylene oligomer, comprising more than 90 mol % propylene and lessthan 10 mol % ethylene wherein the oligomer has: at least 93% allylchain ends, a number average molecular weight (Mn) of about 500 g/mol toabout 20,000 g/mol, an isobutyl chain end to allylic vinyl group ratioof 0.8:1 to 1.35:1.0, less than 100 ppm aluminum, and/or less than 250regio defects per 10,000 monomer units; (vii) a propylene oligomer,comprising: at least 50 mol % propylene and from 10 mol % to 50 mol %ethylene, wherein the oligomer has: at least 90% allyl chain ends, an Mnof about 150 g/mol to about 20,000 g/mol, and an isobutyl chain end toallylic vinyl group ratio of 0.8:1 to 1.2:1.0, wherein monomers havingfour or more carbon atoms are present at from 0 mol % to 3 mol %; (viii)a propylene oligomer, comprising: at least 50 mol % propylene, from 0.1mol % to 45 mol % ethylene, and from 0.1 mol % to 5 mol % C₄ to C₁₂olefin, wherein the oligomer has: at least 90% allyl chain ends, an Mnof about 150 g/mol to about 10,000 g/mol, and an isobutyl chain end toallylic vinyl group ratio of 0.8:1 to 1.35:1.0; (ix) a propyleneoligomer, comprising: at least 50 mol % propylene, from 0.1 mol % to 45mol % ethylene, and from 0.1 mol % to 5 mol % diene, wherein theoligomer has: at least 90% allyl chain ends, an Mn of about 150 g/mol toabout 10,000 g/mol, and an isobutyl chain end to allylic vinyl groupratio of 0.7:1 to 1.35:1.0; (x) a homo-oligomer, comprising propylene,wherein the oligomer has: at least 93% allyl chain ends, an Mn of about500 g/mol to about 70,000 g/mol, an isobutyl chain end to allylic vinylgroup ratio of 0.8:1 to 1.2:1.0, and less than 1400 ppm aluminum; (xi)vinyl terminated polyethylene having: (a) at least 60% allyl chain ends;(b) a molecular weight distribution of less than or equal to 4.0; (c) ag′(_(vis)) of greater than 0.95; and (d) an Mn (¹H NMR) of at least20,000 g/mol; and (xii) vinyl terminated polyethylene having: (a) atleast 50% allyl chain ends; (b) a molecular weight distribution of lessthan or equal to 4.0; (c) a g′(_(vis)) of 0.95 or less; (d) an Mn (¹HNMR) of at least 7,000 g/mol; and (e) a Mn (GPC)/Mn (¹H NMR) in therange of from about 0.8 to about 1.2.
 10. The method of either of claims8 or 9, further comprising the step of contacting the X functionalizedVTM with a hydroxyl, an alkoxide, an aryl anion, a carbanion, a cyano ora phthalimide group.
 11. The method of claim 10, wherein the alcoholgroup for the alkoxide comprises the formula:HOR₁—O—R₂_(n)R₉, wherein R₁ is an alkyl or an aryl; R₂ is a bond, analkyl or an aryl; R₉ is an alkyl or an aryl; and n is from 1 to about500.
 12. The method of claim 10, wherein the alcohol group for thealkoxide comprises the formula:HOR₁—O—R₄_(n)OR₈, wherein each R₁ and R₄ is, independently, an alkylor an aryl; R₈ is, an alkyl or an aryl; and n is from 1 to about 500.13. The method of claim 8, wherein the X functionalized VTM isamorphous.
 14. The method of claim 8, wherein the method provides a 90%yield.
 15. The method of claim 8, wherein the M_(w)/M_(n) of the Xfunctionalized VTM is from 2 to
 4. 16. The method of claim 8, whereinthe M_(w)/M_(n) of the X functionalized VTM is from 1.1 to 1.02.
 17. Thepolyolefin composition of claim 4, wherein the ether group comprises theformula:—OR₁—O—R₂_(n)R₉, wherein R₁ is an alkyl or an aryl; R₂ is a bond, analkyl or an aryl; R₉ is an alkyl or an aryl; and n is from 1 to about500.
 18. The polyolefin composition of claim 4, wherein the ether groupcomprises the formula:—OR₁—O—R₄_(n)OR₈, wherein each R₁ and R₄ is, independently, an alkylor an aryl; R₈ is an alkyl or an aryl; and n is from 1 to about
 500. 19.The polyolefin compositions of claim 2, wherein the composition isamorphous.
 20. The compositions of claim 3, wherein the composition isamorphous.
 21. The composition of claim 4, wherein the composition isamorphous.
 22. The composition of claim 1, wherein the method provides a90% yield.
 23. The composition of claim 1, wherein the M_(w)/M_(n) isfrom 2 to
 4. 24. The composition of claim 1, wherein the M_(w)/M_(n) isfrom 1.1 to 1.02.